UNIVERSITY  OF  CALIFORNIA 
AT   LOS  ANGELES 


THE  OIL  OF  MAIZE 


(ZEA  MAYS) 


HARRIET  WINFIELD,  A.M. 


SUBMITTED  IN  PARTIAL  FULFILMENT  OF  THE  REQUIRE- 
MENTS FOR  THE  DEGREE  OP  DOCTOR  OP  PHILOS- 
OPHY IN  THE  FACULTY  OF  PURE  SCIENCE, 
COLUMBIA  UNIVERSITY. 


NEW  YORK,  1899. 


EASTON.  FA.  : 

THE  CHEMICAL  PUBLISHING  COMPANY. 
1899. 


THE  OIL  OF  MAIZE 


(ZEA  MAYS) 


BY 


HARRIET  WINFIELD,  A.M. 


SUBMITTED  IN  PARTIAL  FULFILMENT  OP  THE  REQUIRE- 
MENTS FOR  THE  DEGREE  OP  DOCTOR  OP  PHILOS- 
OPHY IN  THE  FACULTY  OP  PURE  SCIENCE, 
COLUMBIA  UNIVERSITY. 


NEW  YORK,  1899. 


EASTON.  PA.  : 

IE  CHEMICAL  PUBLISHING  COMPANY. 
1899. 


C8VJ7 


INTRODUCTION. 

The  work  reported  in  this  dissertation  was  undertaken  with 
the  idea  of  investigating  the  many  conflicting  statements  as  to 
the  properties  of  maize  oil  and  of  furnishing  a  more  complete  and 
consistent  record  of  both  its  physical  and  chemical  constants 
than  has  been  heretofore  obtainable. 

This  record  has  been  made  as  complete  as  possible  and  covers 
many  points  on  which  little  work  seems  to  have  been  done  by 
other  investigators.  The  results  obtained  differ  in  several 
important  particulars  from  those  previously  reported  and  offer 
ready  means  for  the  identification  of  the  oil. 

During  the  course  of  the  investigation,  a  method,  which  is 
believed  to  be  new,  was  devised  for  improving  the  oil  for  com- 
mercial purposes.  This  method  frees  the  oil  from  odor  and 
taste  and  relieves  it  of  its  excess  of  free  acid,  at  the  same  time 
rendering  the  oil  more  stable  and  improving  its  drying  qualities. 

For  much  valuable  advice  and  for  samples  which  could  not 
have  been  obtained  elsewhere,  I  am  indebted  to  Dr.  H.  T.  Vult6, 
under  whose  supervision  this  work  has  been  conducted. 


CONTENTS. 

PART  I — DESCRIPTIVE. 

PAGE. 

Occurrence  and  manufacture 5 

General  characteristics 6 

Uses 7 

PART  II — ANALYTICAL. 

Constitution 9 

Physical  Constants. 

Specific  gravity 10 

Viscosity  12 

Index  of  refraction 13 

Chemical  Constants — Quantitative. 

Ash 14 

Free  acid 14 

Iodine  absorption 15 

Saponification  value 17 

Insoluble  acids 18 

Volatile  acids 19 

Acetyl  figure 21 

Glycerol 22 

Unsaponifiable  matter 23 

Chemical  Constants— Miscellaneous. 

Color  reactions  with  sulphuric  acid 24 

Color  reactions  with  nitric  acid 24 

Silver  nitrate  reduction  tests 25 

Miscellaneous  color  reactions 26 

Elaidin 26 

Maumene"  test 27 

Heat  of  bromination 28 

Valenta's  test 29 

Oxygen  absorption 29 

Examination  of  Mixed  Insoluble  Fatty  Acids. 

Preparation  of  acids 30 

Melting-point 30 

Saponification  value 31 

Tabulated  statement  of  constants 31 

Method  for  Improvement  of  Maize  Oil  by  Use  of  Steam. 

Introductory  statement 33 

Description  of  process 33 

Determination  of  constants 34 

Effect  of  treatment 34 

PART  III — SUMMARY. 

Description  of  samples 37 

Tabulation  of  constants 38 

Mathematical  calculations  41 

PART  IV — BIBLIOGRAPHY. 

Chronological  list  of  references 44 

List  of  periodicals  and  abbreviations 48 


THE  OIL  OF  MAIZE. 


PART  I.— DESCRIPTIVE. 

OCCURRENCE  AND  MANUFACTURE. 

The  kernel  of  maize,  or  Indian  corn  as  it  is  generally  known 
in  this  country,  contains  a  larger  percentage  of  oil  than  does  any 
other  grain,  with  the  exception  of  hulled  oats.  It  contains,  in 
round  numbers,  twice  as  much  fat  as  wheat,  three  times  as  much 
as  rye  and  twice  as  much  as  barley.1 

The  per  cent,  of  fat  in  the  whole  kernel  varies  considerably 
with  season  and  locality,  but  is  always  greater  in  sweet  than  in 
field  corn.  The  following  table,  compiled  by  the  U.  S.  Dept.  of 
Agriculture,  shows  the  average  composition  of  American  maize.1 

Field  corn.  Sweet  corn. 

Water 10.75  8.44 

Proteids 10.00  11.48 

Oil 4-25  8.57 

Crude  fibre 1.75  2.82 

Other  carbohydrates 71.75  66.72 

Ash 1.50  1.97 

While  the  whole  kernel  thus  shows  an  unusually  large  amount 
of  oil,  the  percentage  is  much  increased  if  the  germ  alone  be 
taken  into  account.  The  germ  of  Indian  corn  is  a  white,  flat- 
tened, hornlike  body,  much  lighter  than  the  rest  of  the  kernel 
and  can  be  pulverized  only  with  difficulty.  About  14-16  per 
cent,  of  the  whole  grain  is  contained  in  the  germ  and  in  this 
germ  the  amount  of  fat  varies  from  n  per  cent,  to  22  percent. 

The  oil  of  maize  was  first  known  commercially  as  a  bye-prod- 
uct of  distilleries.  The  grain  was  malted  and  mashed  and  the 
oil  was  then  found  floating  on  the  surface  of  the  mash-tubs. 
The  day  before  the  whiskey  was  distilled,  this  oil  was  ladled  off 
and  was  then  purified  by  washing,  filtering,  and  settling.  The 
oil  thus  obtained  was  golden-brown  in  color,  and  was  so  modified 
in  composition  by  impurities  due  to  its  mode  of  preparation,  as 

l  U.  S.  Dept.  Agriculture,  Div.  of  Chem.,  Bull.  50,  13. 


to  be  practically  a  distinct  oil.  This  will  be  seen  by  a  com- 
parison of  its  constants  with  those  of  the  normal  oil. 

The  oil  was  thought  to  affect  injuriously  the  quality  of  the 
whiskey  obtained,  and  various  methods  were  devised  to  effect 
its  removal  before  mashing  the  grain.  Of  these  methods,  the 
most  important  was  that  originated  by  John  Crawford  of  Cincin- 
nati.1 He  extracted  the  oil  from  the  ground  grain  by  the  use  of 
CS,  and  introduced  his  process  into  several  cities  of  the  United 
States.  He  claimed  to  obtain  a  larger  quantity  and  a  higher 
grade  of  whiskey  in  this  way,  but  his  venture  was  not  a  com- 
mercial success. 

A  method  used  for  the  recovery  of  the  oil  from  the  residues  of 
starch  factories  is  also  worthy  of  note.  After  the  deposition  of 
the  starch  from  the  mixture  of  pulverized  corn  and  water,  a 
milky,  easily  putrefiable  liquid  is  left,  which  is  an  emulsion  of 
oil  in  the  dissolved  albuminoids.  A  method  to  separate  and 
recover  both  products  was  devised  by  Dr.  F.  V.  Greene,  and 
patented  March  10,  1885.  Later,  the  John  Scott  Legacy  Medal 
of  the  Franklin  Institute  was  awarded  him  for  his  discovery. 

The  foregoing  methods  have  been  almost  wholly  superseded 
by  the  one  about  to  be  described,  which  is  practically  the  only 
method  for  the  preparation  of  maize  oil  in  use  at  the  present 
time.  The  oil  is  now  an  important  bye-product  in  distilleries 
and  also  in  glucose  and  in  starch  factories.  In  all  these  manu- 
factures, the  grain  is  first  freed  from  the  oil-bearing  germ  by 
Mowery's  Patent  Degerminizer.  This  machine  separates  the 
hard,  light  germ,  first  from  the  crushed  grain,  and  next  from 
the  bran  or  husk,  by  a  process  of  sifting  and  winnowing.  The 
separated  germ  is  then  steamed  to  soften  it  and  the  oil  removed 
by  hydraulic  pressure.  The  oil  thus  obtained  is  purified  only 
by  straining  and  settling,  no  clarifying  or  bleaching  agents  being 
employed  for  the  ordinary  commercial  product.  The  residue, 
or  oil  cake,  is  ground  and  used  for  cattle  feed.  It  is  very 
valuable  for  this  purpose  and  is  exported  in  large  quantities. 

The  manufacture  of  maize  oil  is  assuming  larger  proportions 
yearly  and  is  capable  of  almost  indefinite  extension. 

GENERAL,  CHARACTERISTICS. 

Maize  oil,  when  freshly  made,  is  of  a  pale  straw-yellow  color, 

1  Drug.  Circ.,  1888,  33,  209  ;  J.  U.  Woyd  :  Maize  Oil. 


and  has  a  strongly-marked,  penetrating  odor,  similar  to  that  of 
newly  ground  corn-meal.  The  color  Of  the  oil  is  probably  due 
to  some  oxidation,  as  it  is  much  paler  when  first  made  than  after 
standing  for  some  time  and  develops  a  bright,  golden-yellow 
with  age.  The  oil  recovered  from  the  mash  of  distilleries  is  of 
a  pronounced  golden-brown  color,  due  to  its  mode  of  preparation. 

The  taste  of  the  oil  is  at  first  bland  and  pleasant,  but  is  fol- 
lowed by  considerable  acridity,  lingering  long  on  the  tongue. 
This  taste  is  as  marked  in  an  oil  ten  years  old  as  in  that  freshly 
made. 

A  considerable  variance  of  opinion  as  to  odor  and  taste  is 
shown  by  different  writers  on  the  subject  of  maize  oil,  but  per- 
haps the  most  striking  judgment  is  that  given  by  Bizio,1  the  first 
analyst  to  study  the  oil,  who,  in  1823,  described  it  as  of  a 
"vanilla-like  odor  and  balsamic  taste." 

USES. 

Owing  to  the  almost  unlimited  possible  supply  of  maize  oil, 
and  to  the  cheapness  with  which  it  can  be  produced,  much 
interest  attaches  to  a  consideration  of  the  uses  for  which  it  is 
fitted.  Unfortunately,  the  oil  has  been  known  primarily  as  an 
adulterant  of  more  costly  oils  and,  for  this  reason,  has  been 
seldom  sold  under  its  own  name  in  this  country. 

The  most  important  commercial  application  of  maize  oil  is  its 
use  in  the  manufacture  of  soap.  It  is  peculiarly  fitted  for  this 
purpose,  saponifying  with  great  ease  in  the  presence  of  either 
hot  or  cold  alkali  and  forming  a  light-colored  soap  of  excellent 
quality.  Large  quantities  of  the  oil  are  exported  yearly  for  the 
use  of  the  English  and  Belgian  soap-makers,  but  little  attention 
is  paid  to  it  for  this  purpose  in  America. 

Many  attempts  have  been  made  to  utilize  maize  oil  in  the 
manufacture  of  paint  but,  owing  to  its  lack  of  drying  properties, 
most  of  these  attempts  have  failed  to  produce  anything  but  a 
cheap  grade  of  paint.  In  1887,  however,  Geo.  W.  Banker  suc- 
ceeded in  manufacturing  a  corn-oil  paint  which,  with  the  aid  of 
suitable  dryers,  gave  fairly  satisfactory  results.  Letters  patent 
were  granted  him  in  the  year  named  giving  him  exclusive  rights, 
throughout  Great  Britain,  Canada,  and  the  United  States,  in  the 

i  Chem.  und  Phys.,  37,  377. 


8 

use  of  maize  oil  as  a  vehicle  for  paints,  either  alone  or  in  com- 
bination with  other  oils.  The  specific  claims  made  by.  Mr. 
Banker  on  behalf  of  maize  oil,  are  as  follows :' 

1.  White  paints  do  not  yellow  with  age  but  remain  white. 

2.  Tints,  especially  those  used  for  indoor  work,    are    more 
brilliant  and  durable  than  when  made  up  with  linseed  oil. 

3.  The  paint  is  more  homogeneous,  not  separating  into  two 
portions  as  when  linseed  oil  is  used. 

4.  The  paint  is  smoother  in   application  than  a  linseed  oil 
paint  and  possesses  greater  elasticity. 

Considerable  attention  is  now  being  paid  to  maize  oil  by  the 
grinders  of  paints  and  its  use  in  this  direction  may  be  expected 
to  assume  larger  proportions. 

A  third  use  for  which  this  oil  is  particularly  well  fitted  is  as  a 
substitute  for  olive  oil  in  the  Pharmacopoeia.  In  nearly  all  pre- 
parations in  which  a  fixed  oil  is  necessary,  the  oil  of  maize  is 
equal  or  superior  to  any  other  available  oil,  and  its  use  should  be 
made  officinal.  This  is  notably  true  in  the  case  of  ointments, 
such  as  camphor  cerate,  and  of  ammoniacal  and  lead  liniments.* 

Notwithstanding  the  percentage  of  free  acid  in  maize  oil,  and 
the  marked  action  which  it  has  on  metal,  an  effort  has  been 
made  to  introduce  it  as  a  lubricant  for  machinery.  Three 
patents  were  issued  to  Geo.  W.  Banker,3  in  the  years  1882-1884, 
granting  him  exclusive  rights  for  the  combination  of  : 

1.  Corn  oil,  castor  oil  and  petroleum. 

2.  Corn  oil  with  mineral  oil,  for  lubricating  and  other  purposes. 

3.  Corn  oil  and  castor  oil. 

As  castor  oil  may  be  made  to  combine  with  any  gravity  of 
paraffin,  or  of  crude  or  refined  petroleum,  by  the  use  of  corn 
oil,  any  grade  of  lubricating  oil  may  be  made  in  this  way. 

Maize  oil  has  also  been  used  to  some  extent  as  an  illuminant, 
burning  with  a  white  flame  and  evolving  quite  a  high  degree  of 
heat.  Among  other  uses  which  may  be  named  for  this  oil  are  : 

1.  An  adulterant  for  linseed  and  other  paint  oils. 

2.  An  adulterant  for  lard. 

3.  An  adulterant  for  olive  and  other  salad  oils. 

4.  A  vehicle  for  the  introduction  of  coloring-matter  into  butter. 

5.  A  substitute  for  linseed  oil  in  the  manufacture  of  putty. 

1  Oil,  Paint  and  Drug  Reporter,  Oct.  12,  1891. 

2  Heinitsh  :  Pharm.  Rec.,  1889,  9,  236;  Lloyd  :  Drug.  Circ.,  1888,  32,  209. 
8  Oil,  Paint  and  Drug  Reporter,  Oct.  12,  1891. 


PART  II.— ANALYTICAL. 

CONSTITUTION. 

Although  the  actual  separation  and  determination  of  the  mixed 
fatty  acids  contained  in  maize  oil  have  not  been  attempted  in 
the  present  investigation,  certain  inferences  as  to  the  constitution 
of  the  oil  have  resulted  from  observations  made  during  the  prog- 
ress of  the  work.  These  inferences,  together  with  a  brief 
resume  of  the  work  done  in  this  line  by  other  analysts,  may  be 
found  of  some  interest  at  this  point. 

The  presence  of  a  volatile  oil,  with  a  "peculiar  grain-like 
odor,"  has  been  recognized  by  nearly  all  observers.  This  vola- 
tile oil  is  very  characteristic  of  the  oil  of  maize,  but  maybe  easily 
and  completely  driven  off  by  a  steam  distillation  at  the  ordinary 
pressure,  leaving  the  oil  free  from  all  objectionable  odor  and 
taste. 

In  the  year  1866,  Hoppe-Seyler1  succeeded  in  isolating  stearic, 
palmitic, and  oleic  acids  from  maize  oil  and  the  existence  of  these 
acids  has  since  been  confirmed  by  many  observers.  Rokiti- 
ansky,*  in  1894,  added  linolic  acid  to  those  previously  deter- 
mined and  succeeded  in  obtaining  its  oxidation  product,  sativic 
or  tetraoxystearic  acid.  The  presence  of  linolic  acid  is  con- 
firmed by  a  late  observer,  C.  G.  Hopkins,3  of  Cornell  University, 
who  finds  a  large  percentage  of  this  acid  in  maize  oil. 

Rokitiansky1  also  asserts  the  presence  of  a  hydroxylated  acid 
(probably  ricinoleic)  in  the  solid  fatty  acids,  and  this  result  is 
confirmed  by  the  somewhat  high  acetyl  figure  of  the  oil.  The 
evidence  of  the  existence  of  linolenic  acid  is  thus  far  negative 
and  the  only  insoluble  fatty  acids,  whose  presence  in  maize  oil 
can  be  affirmed  with  any  degree  of  certainty  are  : 

1.  Palmitic  acid  =  C16H3,O.,  =  C16H81COOH. 

2.  Stearic  acid  =  C18H86O,  -  C17H36COOH. 

3.  Oleic  acid  =  C18H34O,  =  C^H^COOH. 

4.  Linolic  acid  =  C18H,,O,  =  C17H31COOH. 

5.  Ricinoleic  acid  =  C18H34O3  —  C17HM(OH)COOH. 
Comparatively  little  attention  has  been  paid  to  the  volatile 

acids  of  maize  oil,  certain  observers  going  so  far  as  to  deny  their 

1  Bull.  Soc.  Chim.  (1866),  fa]  6,  342. 

2  Ph.  Russ.  (1894),  712-713. 

8  J.  Am.  Chem.  Soc.,  Dec.,  1898. 


existence.  Rokitiansky,1  however,  has  succeeded  in  obtaining 
proof  of  the  presence  of  formic  acid,  and  also  asserts  thatcaproic, 
caprylic,  and  capric  acids  are  probably  to  be  found  in  the  oil.  A 
steam  distillation  of  the  mixed  fatty  acids,  during  the  course  of 
the  present  investigation,  disclosed  the  presence  of  a  notable 
amount  of  some  acid,  volatile  in  steam,  but  insoluble  in  water. 
This  is  probably  lauric  acid. 

The  following  points  are  indications  that  homologues  of  the 
acetic  series,  lower  than  lauric  acid,  are  to  be  found  in  maize  oil : 

1.  The  high  Reichert  value. 

2.  The  high  percentage  of  glycerine. 

3.  The  ease  with  which  partial  dissociation  of  the  oil  takes 
place  under  the  influence  of  steam  at  the  ordinary  pressure. 

4.  The  fact  that  the  aqueous  liquid,  obtained  by  washing  the 
mixed  fatty  acids  with  boiling  water  and  decanting  through  a 
filter,  shows  a  marked  acid  reaction  to  phenolphthalein,  after 
having  been  made  neutral  to  methyl  orange. 

The  probable  presence  of  the  following  volatile  acids  in  maize 
oil  may,  therefore,  be  affirmed.  Much  further  investigation, 
however,  is  necessary  to  establish  its  constitution,  both  in  regard 
to  the  soluble  and  to  the  insoluble  fatty  acids. 

1.  Formic  acid  =  CH,O,  =  HCOOH. 

2.  Caproic  acid  =  C.H.,0,  =  CBHS1COOH. 

3.  Caprylic  acid  =  CeH16Oa  =  C,H16COOH. 

4.  Capric  acid  =  C10H,0Oa  =  C9H19COOH. 

5.  Laurie  acid  =  ClfH,A  =  CnHMCOOH. 

The  unsaponifiable  matter  consists  almost  wholly  of  phyto- 
sterol  or  phytosteryl  alcohol, 

C26H440  =  C,.H41OH, 
and  the  amount  contained  is  very  characteristic  of  the  oil. 

DETERMINATION  OF  SPECIFIC  GRAVITY. 

Description  of  Method. 

A.  Sprengel  Tube. — The  tubes  used  in  this  determination  were 
made  in  the  usual  shape,  from  small  glass  tubing  and  supplied 
with  a  platinum  wire  by  which  to  suspend  them  from  the  bal- 
ance hook. 

1  Ph.  Russ.  (1894),  712-713. 


II 

Each  tube  was  weighed,  filled  with  distilled  water  at  15.5°  C. 
and  again  weighed.  It  was  then  carefully  dried,  cooled,  filled 
with  the  oil  at  15.5°  C.  and  again  weighed,  thus  affording  data 
for  the  determination  of  the  specific  gravity  at  15.5°  C. 

In  order  to  obtain  the  specific  gravity  at  100°  C.,  the  Sprengel 
tube,  filled  with  oil,  was  placed  in  the  neck  of  an  Erlenmeyer 
flask,  in  such  a  manner  that  the  capillary  arms  of  the  tube  were 
supported  by  the  neck  of  the  flask.  The  tube  was  then  sub- 
jected to  the  ^action  of  boiling  water  until  oily  drops  ceased  to 
ooze  from  the  capillaries,  when  it  was  again  dried,  cooled  and 
weighed.  The  oily  drops  were  removed  as  they  appeared  by  a 
piece  of  filter-paper.  The  weight  of  the  oil  at  100°  C.  was  com- 
pared with  that  of  distilled  water  at  15.5°  C. 

B,  Westphal  Balance. — This  method,  although  it  can  be 
quickly  applied,  does  not  compare  in  accuracy  with  that  by 
means  of  the  Sprengel  tube.  In  fact,  very  little  reliance  can 
be  placed  on  it  beyond  the  second  place  of  decimals. 

In  obtaining  the  specific  gravity  at  100°  C.  by  this  method,  a 
solid  thermometer  body  was  used,  and  the  tube  containing  the 
oil  was  immersed  in  boiling  water,  no  attempt  being  made  to 
take  the  gravity  until  the  oil  was  uniformly  at  100°  C.  Still 
more  variation  was  observed  when  using  the  Westphal  at  this 
temperature  than  at  15.5°  C. 

RESTJI/TS   OBTAINED. 
A.  PHOENIX  PAINT  Co.  Oil,.1 

Wt.  water        Wt.  oil          Wt.  oil 

15.5°  C.  15.5°  C.          100"  C.  Sp.  gr.  Sp.  gr. 

Grams.         Grams.        Grains.  15.5°  C.  100°  C. 

I 1-5265          1.4068          I.33I5  0.9216  0.8722 

II 1.6404          I.5H3          L4297  0.9213  0.8715 

III 1.3602          1.2528          1.1848  0.9210  0.8710 

Average  for  Sprengel  tube 0.9213  0.8716 

Westphal  balance 0.921  0.895 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OiL.2 

I 2.0130        1.8547        1-7554       0.92136      0.87203 

II 2.1788        2.0072        1.8958       0.92124      0.87011 

Average  for  Sprengel  tube 0.9213        0.87107 

Westphal  balance 0.921 

1  Ten-year-old  sample  of  oil  expressed  by  hydraulic  pressure. 

2  Fresh  sample  of  oil  expressed  by  hydraulic  pressure. 


12 

i    C.  DISTILLERY  OIL.' 

Wt.  water        Wt.  oil          Wt.  oil 

15-5°  C.          15.5*  C.           100°  C. 

Sp  gr. 

Grams.          Grams,         Grams. 

15-5°  C. 

J 

I  OO2.7          O  0288          O  8?8<i 

n  o?ci 

II 

T    C*7lR               T    /ICCT               T    77&O 

^yoo 

O  O2C7 

Average  for  Sprencrel  tube  ••••••  .  •  •  .  • 

u'  y-o  / 

O  Q2^^ 

Westnrial  balance.  .  . 

Sp.  gr. 
loo"  C. 
0.8746 
0.8767 
0.8756 


COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 


Sp.  gr. 
at  15°  C. 

0.8360 

0.9160 

0.9170 

0.9200 

0.9215 

0.9216 

0.9215-0.9244 

0.9220 

0.9239 

0.9238-0.9262 
0.9243 
0.9244 
0.9245 

0.9262 


Observer. 
Rokitianski* 
Curtmann 
Bowers2 
Shuttleworth 
Schaedler 
Procter 

De  Negri  and  Fabris 
Trimble 
Hart3 
Hopkins 
Duliere 
Smith 
DeNegri2 
Mills 


Reference. 

Ph.  Russ.  (1894),  712-713. 
Chem.  Centrbl.,  59,  1193. 
Pharm.  J.,  Nov.,  1889. 
Pharm.  J.,  16,  1095. 
J.  Soc.  Chem.  Ind.,  n,  504. 
J.  Soc.  Chem.  Ind.,  17,  n. 
Ztschr.  anal.  Chem.,  33,  547-72. 
Am.  J.  Pharm.,  58,  265. 
Chem.  Ztg.,  17,  1522. 
J.  Am.  Chem.  Soc.,  Dec.,  1898. 
J.  Pharm.  (1897),  217. 
J.  Soc.  Chem.  Ind.,  n,  504-5. 
Chem.  Ztg.,  22,  961-976. 
J.  Soc.  Chem.  Ind.,  u,  504-5. 


DETERMINATION  OF  VISCOSITY. 


Process. 

This  determination  was  made  by  means  of  a  Boverton  Red- 
wood viscosimeter.  The  viscosity  was  taken  at  20°  C.  and  the 
instrument  carefully  standardized  for  both  distilled  water  and 
rape  oil  at  this  temperature.  The  time  of  flow  for  50  cc.  oil  was 
noted  by  means  of  a  stop-watch  and  six  readings  were  made  for 
each  sample.  Great  care  was  taken  to  avoid  any  change  of 
temperature  during  the  operation. 

Specific  Viscosity. 

Distilled  Water  as  Standard. — Time  of  flow  for  50  cc.  oil  as 
compared  with  that  of  equal  volume  of  distilled  water  at  the 
same  temperature. 

Rape  Oil  as  Standard. — Viscosity  determined  in  manner  sim- 
ilar to  that  used  with  water-standard,  but  a  correction  applied 
by  multiplying  the  result  by  the  ratio  of  the  density  of  the  oil 
under  examination  to  that  of  rape  oil.  Viscosity  of  rape  oil 
taken  as  100. 

1  Kffteen-year-old  sample  of  oil  from  mash  of  distillery. 

2  Petroleum  ether  extract.  3  Dark  brown  oil. 


13 
RESULTS  OBTAINED. 

Av.  time 

Tempera-    of  flow.  Viscos.  Viscos. 

ture.       Seconds.  water.  rape  oil. 

Distilled  water 20°            29  i.oo          

Rape  oil 20°         405.5          100.00 

Phoenix  oil 20°         283.7  9-79          70.42 

Glucose  sugar  oil 20°         297.7  10.27          73-89 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Tempera-  Viscos.        Viscos.  • 

ture.  water.         rape.          Observer.  Reference. 

18°  C.-I90  C 61.1          Smith        J.  Soc.  Chem.  Ind.,  xi,  504. 

15°  C.  19.2  And£s       Veg.  Fats  and  Oils. 

Viscosity  of  almond  oil  Shuttleworth  Pharm.  J.,  16,  1095. 

Viscosity  greater  than  olive  Bowers      Pharm.  J.,  Nov.,  1889. 

DETERMINATION  OP  INDEX  OF  REFRACTION. 

The  instrument  used  for  this  determination  was  Abbe's  Refrac- 
tometer. 

A.  PHOENIX  PAINT  Co.  OIL. 

Temperature.  A.  T. 

1 15°  C.  1.4768  35-8 

II 15°  C.  1.4766  36.0 

III 2o°C.  1.4762  35.9 

IV 20°  C.  1.4760  35.9 

Average  for 15°  C.  1.4767  35-9 

Average  for 20°  C.  1.4761  35.9 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 

1 15°  C.  1.4765  35-8 

II 15°  C.  1.4766  36.0 

III 15°  C.  1.4767  36.0 

Average  for 15°  C.  1.4766  35.9 

C.  DISTILLERY  OIL. 

1 19-5°  C.  1-4767  36-2 

II 2o°C.  1.4766  36.2 

III 2o.5°C.  1.4764  36.3 

Average  for 20°  C.  1-4765  36-2 


COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

tmpera-       Refractive 
ture.  index.  Observer.  Reference. 

15°  C.          1.4765  Procter          J.  Soc.  Chem.  Ind.,  17,  n. 


14 

DETERMINATION   OF  ASH. 

Process, 

The  oil  was  weighed  into  a  small,  flat- bottomed  platinum  dish, 
and  the  operation  conducted  in  the  usual  manner,  care  being 
taken  to  employ  as  low  a  temperature  as  possible.  The  odor  of 
the  volatile  oil  was  very  marked  at  first  but  soon  entirely  dis- 
appeared. The  oil  burned  with  a  very  bright  flame  and  com- 
paratively little  smoke. 

RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  OIL. 


I  

Wt.  oil. 
Grams. 

Wt.  ash.               Asb. 
Gram.             Per  cent. 

II  

2  2665 

B.  DISTILLERY  OIL. 

I 0.6750          o.ooii          0.065 

II 0.6005          0.0004          0.066 

Average 0.0655 

DETERMINATION  OF  FREE  ACID. 
Process. 

Five  to  ten  grams  oil  were  carefully  weighed  into  a  4-oz.  flask. 
50-100  cc.  of  a  mixture  of  9  parts  95  per  cent,  alcohol  and  i  part 
ether  were  neutralized  with  aqueous  w/io  KOH,  phenol- 
phthalein  indicator,  and  added  to  contents  of  flask.  The  flask 
was  then  heated  on  a  water-bath  until  the  solution  of  the  oil  was 
as  nearly  perfect  as  possible,  and  the  liquid  in  the  flask  was 
finally  titrated,  while  still  warm,  with  n/io  KOH. 
Acid  Value. 

Number  mg.  KOH  necessary  to  neutralize  i  gram  oil. 
Per  Cent.  Free  Acid. 

This  constant  was  calculated  to  oleic  acid. 
Degrees  of  Acidity. 

Number  cc.  «/KOH  required  to  neutralize  100  grams  oil. 
Action  on  Copper. 

Bright  copper  wire  was  immersed  in  the  oil  and  allowed  to 
remain  for  several  days.  Marked  discoloration  was  shown  by 
all  three  oils,  the  glucose  sugar  oil  being  the  least  affected. 


15 

RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  OIL. 

Wt.  oil.   Vol.n/ioKOH.     Acid  Free  acid.  Degrees 

Grams.                cc.              value.  Per  cent.  acidity. 

I 10.6617               7.0              3.68               1.851  6.56 

II 7-2552            4-8            3-7i            1-851  6.62 

Average 3.70            1.851  6.59 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 

1 9-9294  4-o  2.26  1.136  4.03 

II 13.0816  5.2  2.23  1. 121  3.97 

Average 2.25  1.128  4.00 

C.  DISTILLERY  OIL. 

1 4-2351         15.6         20.64  10.387  36.83 

II 6.2726         23.1         20.66  10.385  36.83 

Average 20.65  10.386  36.83 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Per  cent,  free  acid.  Observer.  Reference. 

0.75  Hart2  Chem.  Ztg.,  17,  1522. 

0.88  Lloyd  Chem.  Centrbl.,  59,  257. 

o.oo  Spiiller3  Eingl.,  264, 626. 

5.65  De  Negri1  Chem.  Ztg.,  22, 961-976. 

DETERMINATION  OP  IODINE  ABSORPTION. 

Description  of  Method. 

A.  Necessary  Solutions. 

1 .  HgCl,  in  95  per  cent,  alcohol  —  60  grams  per  liter. 

2.  Iodine  in  95  per  cent,  alcohol  =  50  grams  per  liter. 

The  alcohol  used  in  making  up  these  solutions  was  purified  by 
oxidation  with  K5Mn.,O8  and  subsequent  distillation  over  pul- 
verized CaCOs.  The  distillate  was  rejected  until  no  discolora- 
tion from  aldehyde-resin  was  shown  on  heating  a  small  portion 
with  a  lump  of  solid  KOH  for  ten  minutes  in  boiling  water. . 

3.  »/ioNa,S,Ot- 

This  solution  was  standardized  by  w/so  K,Cr.,O7  and  proved 
to  contain  24.3137  grams  of  Na,S2Oj. 

4.  Twenty  per  cent.  KI  solution  made  up  with  distilled  water. 

5.  Solution  of  boiled  starch  as  indicator. 

B.  Process. 

i  Petroleum  ether  extract.  a  Dark-brown  oil.  *  Ether  extract. 


i6 

Thin  Brlenmeyer  flasks,  having  accurately  fitted  ground  glass 
stoppers  and  flaring  mouths,  thus  forming  a  gutter  between  flask 
and  stopper,  were  used  for  this  operation. 

Equal  parts  of  solutions  i  and  2  were  mixed  24  hours  before 
each  test  and  allowed  to  stand  in  the  dark  until  needed. 

About  0.250  gram  oil  was  weighed  into  each  flask,  the  oil  dis- 
solved in  10  cc.  chloroform  and  25  cc.  of  the  mixed  Hiibl  solu- 
tion added.  The  flask  was  then  stoppered,  the  gutter  filled 
with  KI  solution  and  the  whole  set  away  in  the  dark  for  24 
hours.  A  blank  test  was  run  for  every  determination. 

After  24  hours  the  stopper  was  removed  and  distilled  water 
added  to  contents  of  flask  until  of  convenient  bulk  for  titration. 
KI  solution  was  also  added,  sufficient  to  dissolve  any  precipi- 
tated Hgls.  The  liquid  was  then  titrated  with  n/io  Na,S5O3 
until  colorless,  a  few  drops  of  starch  indicator  being  added  when 
color  had  nearly  disappeared. 

RESULTS  OBTAINED. 


I 

A.  PHOENIX  PAIN' 

Wt.  oil.              Vol.  hypo. 
Gram.                      cc. 

r  Co.  OIL. 

Wt.  iodine.      Iodine  absorption. 
Gram.                    Per  cent. 

o.235323                118.44 
0.295088                 119.66 
°-323725                120.90 
0.273921                119.95 

II... 

Ill  . 

IV  • 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 

I  ...........  0.2708  26.2  0.322183 

II  ..........  0.2441               23.3               0.290108  118.85 

III  .........  0.2697               25.7               0.319990  118.65 

IV  .........  0.3070               29.1                0.326232  118.02 

Average  Hiibl  figure  ..........................  1  18.62 

C.  DISTILLERY  OIL. 

I  ...........  0.2199              20-1              0.250264  113.80 

II  ..........  0.2894              26.2              0.326215  112.72 

III  .........  0.2559              23.4              0.291352  113-85 

IV  .........  0.2453                22-2                0.276471  112.70 

Average  Hiibl  figure  ..........................  113.27 


COMPARISON  WITH  RESUI/TS  OF  OTHER  OBSERVERS. 

Hiibl  figure.  Observer.  Reference. 

75.8  Rokitianski1  Ph.  Russ.  (1894),  712-713. 

111.2-123  De  Negri  and  Fabris        Ztschr.  anal.  Chem.,  33,  547-72. 

115.17  De  Negri1  Chem.  Ztg.,  22,  961-976. 

116.3  Smetham  Anal.,  18,  191-193. 

117  Hart2  Chem.  Ztg.,  17,  1522. 

119.6  Hazura  Ztschr.  angew.  Chem.  (1888),  696. 

119.4-119.9  Spiiller3  Dingl.,  264, 626. 

121.7-122.7  Lane  J.  Chem.  Soc.  (1893),  A,  153. 

122  Hehner  J.  Soc.  Chem.  Ind.,  16,  87. 

122  Wallenstein  Chem.  Ztg.  (1894),  18,  (ii),  119. 

121.5-123.1  Hopkins  J.  Am.  Chem.  Soc.,  Dec.,  1898. 

122.55  Dulidre  J.  Pharm.  (1897),  217. 

122.9  Mills  J.  Soc.  Chem.  Ind.,  u,  504. 

DETERMINATION  OP  SAPONIFICATION  VALUE. 
Koettstorfer  Process. 

About  2.5  grams  of  oil  were  weighed  into  a  4-oz.  flask  and 
25  cc.  alcoholic  potash,  approximately  half-normal,  and  made 
from  alcohol  purified  as  described  under  Hiibl  process,  were 
added.  A  blank  test  was  also  run  on  an  equal  amount  of 
alcoholic  potash  in  a  similar  flask.  Blank  and  test  were  covered 
with  watch-glasses,  to  avoid  contamination  by  CO3,  and  evapo- 
rated to  complete  dry  ness  on  a  water-bath.  75  cc.  neutral 
alcohol  were  next  added  to  the  contents  of  each  flask,  heat 
applied  until  solution  was  perfect  and  liquid  titrated,  while  still 
warm,  until  w/HCl,  phenolphthalein  indicator.  The  blank  was 
titrated  first,  on  account  of  its  greater  liability  to  contamination 
by  CO,. 

Saponification  Value  or  Koettstorfer  Figure. 

Number  of  mg.  of  KOH  necessary  for  saponification  of  one 
gram  of  oil. 

Saponification  Equivalent. 
Number  of  mg.  of  oil  equivalent  to  i  cc.  w/KOH. 

1  Petroleum  ether  extract. 

2  Dark  brown  oil. 
8  Ether  extract. 


i8 


RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  OIL. 

Wt.  oil.    Vol.  n/HCl.  Koettstorfer 
Grams.  cc.  fig. 

I  ................    2.OI27          6.95  I93-7I 

II  ...............    2.5187          8.60  I9L55 

III  ..............    2.4600          8.45  192.70 


Average 


192.65 


Sapon. 
equiv. 

289.61 
292.88 
291.13 
291.21 


B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 


I  .........  ,  ......  3.8356  13.20 

II  ...............  5-2317  18.05 

III  ..............  2.56:1  8.75 

Average 


193-07 
193.55 

191-31 
192.64 

C.  DISTILLERY  OIL. 

I  ................  1.9700       6.75         190.29 

II  ...............  2.2206       7.65         193.26 

Average  ....................  i9T-78 


Ether 
value. 

190.01 
187.85 
189.00 
188.95 


290.57  190.82 

289.85  191.3° 

293.24  189.06 

291.22  190.39 


294.81  169.64 
290.28  172.61 
292.55  171-13 


COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 


Sapon. 
equiv. 


Chem.  Ztg.,  22,  961-976. 


Koettstorfer 
fig. 

182.81  306.9  De  Negri1 

188.1-189.2  298.3-296.6  Spiiller3  Dingl.,  264,  626. 

188-193         298.4-290.7  De  Negri  and  Fabris    Ztschr.  anal.  Chem.,  33,  547. 

189.5  296  Hart*  Chem.  Ztg.,  17,  1522. 

193.4  290.07  Mills  J.  Soc.  Chem.  Ind.,  11,504. 

198.5  282.6  Smetham  Anal.  18,  191-193. 
198.8-203     282.2-276.4  Duliere  J.  Pharm.  (1897),  217. 


DETERMINATION  OF  INSOLUBLE  FATTY  ACIDS. 
Hehner  and  Angeir  s  "  Wash  Process.11 

2-4  grams  oil  were  dissolved  in  ether  in  a  beaker.  50  cc. 
of  alcoholic  potash  (made  03'  dissolving  about  20  grams  KOH 
in  500  cc.  purified  aud  redistilled  95  per  cent,  alcohol),  were 
added  to  ether  solution  of  oil  and  the  whole  heated  on  a  water- 
bath  until  saponification  was  effected.  The  liquid  was  then 
diluted  with  hot  distilled  water  and  heated  until  the  ether 
and  alcohol  were  entirely  expelled.  The  aqueous  soap  solution 
thus  formed  was  broken  up  with  dilute  HC1  and  heating  con- 
tinued until  insoluble  fatty  acids  formed  a  clear  oily  layer. 


l  Petroleum  ether  extract. 


2  Dark  brown  oil. 


*  Ether  extract. 


19 

The  liquid  was  then  chilled  until  fatty  acids  were  solidified 
and  the  watery  portion  decanted  through  an  ashless  filter.  Boil- 
ing water  was  added  to  fatty  acids  remaining  in  beaker 
and  chilling  and  decanting  repeated.  Process  was  continued 
until  filtrate  was  neutral  to  methyl  orange.  Fatty  acids  were 
finally  transferred  to  filter  and  allowed  to  run  through  into  tared 
flask.  Filter  was  washed  out  with  ether,  this  expelled  from 
flask  in  an  air-bath  and  the  flask  was  then  cooled  and  weighed. 

RESUI/TS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  OIL. 

Wt.  oil  taken.    Wt.  insol.  fatty  acids.        Hehner. 
Grams.  Grams.  value. 

1 4.6700  4-3256  92.63 

II 2.6092  2.4121  92.45 

III 2.3161  2.1609  93-29 

Average  Hehner  value 92.79 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 

1 3-5853  3-2678  91.14 

II 3-2331  3-0142  93-23 

III 2.6079  2.4079  92.33 

Average  Hehner  value 92.23 

C.  DISTILLERY  OIL. 

1 3-9832  3-5102  88.12 

II 2.8297  2.4995  88.30 

Average  Hehner  value 88.21 

-  COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Hehner  value.          Observer.  Reference. 

93.40        Hoppe-Seyler2  Bull.  Soc.  chim.  (1866),  [2],  6,  342. 

93.57        Hopkins  J.  Am.  Chem.  Soc.,  Dec.,  1898. 

94.70        Spiiller*  Dingl.,  264,  626. 

95.70        Hart1  Chim.  Ztg.,  17,  1522. 

96.70        Lloyd  Chem.  Centrbl.,  59,  1193. 

DETERMINATION   OF  VOLATILE  ACIDS. 
Reichert  (Modified}  Process. 

Precisely  2.5  grams  oil  were  weighed  into  a  small  wide-mouthed 
flask  and  saponified  by  25  cc.  of  approximately  half-normal  alco- 
holic potash,  as  in  the  Koettstorfer  process,  evaporating  off  the 
alcohol  completely.  The  alcohol  used  in  this  determination  was 

1  Dark  brown  oil.  a  Ether  extract. 


20 

purified  as  described  under  the  Hiibl  process.  50  cc.  distilled 
water,  containing  i  cc.  phenolphthalein  indicator,  were  then 
added  to  the  dried  soap  and  the  whole  heated  on  the  water-bath 
until  the  soap  was  completely  dissolved.  While  still  warm,  the 
aqueous  soap  solution  was  titrated  with  n/2  HSSO4,  overrunning 
2  cc.  The  decomposed  soap  solution  was  then  slowly  distilled 
into  a  similar  flask,  containing  50  cc.  of  n/io  KOH  plus  i  cc. 
phenolphthalein  indicator.  Great  care  was  used  to  prevent  any 
of  the  liquid  being  carried  over  into  the  receiver.  A  large  per- 
centage of  a  solid  fatty  acid  also  distilled  over  in  white  flakes, 
but  was  held  back  by  a  small,  wetted  filter,  placed  in  the  neck 
of  the  receiving  flask. 

When  about  50  cc.  of  the  liquid  in  the  distilling  flask  had  gone 
over,  50  cc.  more  of  distilled  water  were  added  to  the  residue 
and  the  distillation  repeated.  The  contents  of  the  receiver  were 
then  titrated  back  with  n/io  HC1  and  the  "  Reichert  Figure  " 
calculated  from  the  amount  of  volatile  acids  thus  recovered  from 
the  two  distillations. 

Reichert  Figure. 

Number  of  cc.'s  of  n/io  KOH  neutralized  by  the  volatile  acids 
recovered  from  two  distillations  of  the  fatty  acids  from  2.5  grams 
oil. 

RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  OIL. 

Wt.  KOH  for  loo  g.  oil. 
Vol.  «/10HCl.         Reichert  figure.  Gram. 

I  45-8  4-2  0.94248 

II 45-6  4-4  0.98736 

Average 4-3  0.96492 

R.  GLUCOSE  SUGAR  REFINING  Co.  OIL. 

I 46.0  4.0  0.89760 

II 45-6  4-4  0.98736 

Average 4-2  0.94248 

COMPARISON  WITH  THE  RESULTS  OF  OTHER  OBSERVERS. 

Reichert  value.  Observer.  Reference. 

0.33  Spiiller  Dingl.,  264,626. 

2.51  Smith  J.  Soc.  Chem.  Ind.,  ix,  504. 

6-7*  Morse  N.  H.  Expt.  Sta.  Bull.  (1892),  16,  19. 

o.o  Hopkins  J.  Am.  Chem.  Soc.,  Dec.,  1898. 

i  Calculated.  100  parts  oil  require  0.56  parts  KOH. 

«  Calculated.  Reported  as  3.2  per  cent,  volatile  acids. 


C.  DISTILLERY  OIL. 

Wt.  KOH  for 

100  g.  oil. 
Vol.  n/10HCl.      Reichert  figure.  Grams. 

I 39-9  IO.I  2.26644 

II 40.3  9.7  2.17668 

Average 9.9  2.22156 

DETERMINATION  OF  ACETYL  VALUE. 
Process. 

About  50  grams  oil  were  placed  in  a  round-bottomed  flask, 
together  with  an  equal  volume  of  acetic  anhydride,  the  flask 
attached  to  an  inverted  condenser  and  its  contents  slowly  boiled 
for  two  hours.  The  acetylated  oil  was  next  transferred  to  a 
large  beaker,  several  hundred  cc.  of  distilled  water  added  and 
the  liquid  heated  to  the  boiling-point  for  about  half  an  hour. 
The  contents  of  the  beaker  were  then  transferred  to  a  separator, 
the  aqueous  layer  drawn  off,  the  acetylated  oil  washed  with  boil- 
ing water  until  acid-free  (methyl  orange  indicator),  filtered 
through  a  dry  filter  and  dried  in  an  air-bath  at  100°  C. 

2-4  grams  of  the  dried,  acetylated  oil  were  now  saponified 
with  alcoholic  potash,  a  blank  being  run  to  ascertain  the  titre  of 
the  potash  used  and  care  taken  not  to  heat  the  liquid  longer  than 
was  necessary  for  saponification.  The  Koettstorfer  figure  was 
then  ascertained  in  the  usual  manner  by  titration  with  «/HCl. 
Enough  additional  rc/HCl  was  then  run  into  the  liquid  to  make 
the  total  amount  of  acid  exactly  correspond  to  the  titre  of  the 
alcoholic  potash  used.  The  oily  layer  was  next  filtered  off  and 
washed  until  acid-free  as  in  the  Hehner  process.  Finally  the  fil- 
trate and  washings  were  titrated  with  rc/KOH. 

Acetyl  Value. 

Number  of  mg.  KOH  necessary  to  neutralize  acetic  acid 
resulting  from  saponification  of  one  gram  of  acetylated  oil. 

RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  OIL,. 


I 

Wt.  oil. 
Grams. 

Vol. 
n/HCl. 
cc. 

8  8 

Koettstorfer 
fig- 
2IO  8 

Vol. 
«/10KOH 
cc. 

Acetyl  value. 
10.78 

11 

7  6 

4  I 

11-45 

Average  

••    21  1.  5 

II.  12 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 


I 

Wt.  oil. 
Grains. 
!  8641 

Vol. 
n/HCl. 
cc. 

Koettstorfer 
fig- 
21^  7 

Vol. 
n/IOKOH. 
cc. 
•i  7 

Acetyl  value. 
11.14 

II.  . 

x  4686 

C    c 

2IO.I 

•3    I 

11.84 

...     211.  Q 

II.4Q 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Koetts-  Acetyl  value 
torferfig.      (filtr.).  Observer.  Reference. 

201.5        8-25        Lewkowitsch         Allen:  Com.  Org.  Anal.,  2,  68. 
200.9        7-9°        Lewkowitsch         Allen:  Com.  Org.  Anal.,  2,  68. 

DETERMINATION  OF  GLYCEROL. 
Hehner" 's  Dichromate  Method. 
Solutions. 

1.  K.jCr.,0,  =  74.86  grams  per  liter. 

2.  KaCr.,O7  =  7.486  grams  per  liter. 

3.  FeSO4.(NH4)2SO4.6HaO  =  about  240  grams  per  liter. 
Solution  i  was  made  with  the  utmost  care  from   KaCraO7  of 

known  purity,     i  cc.  of  this  solution  corresponds  to  0.010025 
gram  of  glycerol. 

Solution  3  was  standardized  on  solution  2  ;  a  little  HaSO4  was 
added  to  the  solution  to  prevent  decomposition. 

Process. 

2-3  grams  oil  were  saponified  with  alcoholic  potash  and  the 
soap  solution  at  once  diluted  to  about  200  cc.,  the  alcohol  not 
being  driven  off  on  account  of  danger  of  loss  from  volatilization 
of  glycerol.  The  soap  was  then  decomposed  by  dilute  HaSO4, 
the  liberated  fatty  acids  filtered  off  and  washed  until  acid-free 
and  the  filtrate  and  washings,  amounting  in  all  to  about  i  liter, 
reduced  to  250  cc.  by  evaporation. 

50  cc.  of  the  stronger  dichromate  solution  and  25  cc.  of  con- 
centrated HaSO4,  suitably  diluted,  were  next  added  to  the  glyc- 
erol solution  and  the  whole  heated  on  a  water-bath  for  about 
two  hours.  The  liquid  was  then  titrated  with  an  excess  of  the 
ferrous  solution  and  this  excess  titrated  back  with  the  dilute 
dichromate  solution,  potassium  ferricyanide  indicator. 


23 

RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  Oil,. 

Wt.  oil.  Vol.  K,Cr,0T.        Wt.  glycerol.  Glycerol. 

Grams.  cc.  Grams.  Per  cent. 

1 2.6092  27.57  0.276395  10.59 

II 2.3361  24.46  0.245217  10.50 

Average 10.545 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  OIL. 

1 2.5701              26.37              0.264359  Jo.29 

II 2.0425              21.21              0.212635  10.41 

Average 10.35 

DETERMINATION  OF  PHYTOSTEROI,. 
Process  of  Foster  and  Reichelmann . 

50  grams  oil  were  weighed  into  a  round- bottomed  flask,  75  cc.  of 
95  per  cent,  alcohol  added  and  the  mixture  boiled  for  5  minutes 
under  a  reflux  condenser.  While  hot,  the  alcohol  was  decanted 
through  a  filter,  aud  the  oil  was  then  treated  with  a  fresh  portion 
of  alcohol.  The  alcoholic  filtrate  was  next  saponified  with  an 
excess  of  aqueous  potash,  the  resultant  soap  evaporated  to 
dryness  and  the  residue  extracted  with  successive  portions  of 
ether. 

The  ether  extract  was  evaporated  to  dryness  and  the  residue 
of  crude  phytosterol  estimated  as  unsaponifiable  matter.1  The 
residue  was  then  treated  with  a  little  ether,  the  resultant  solution 
filtered  and  ether  evaporated,  this  second  residue  taken  up  with 
95  per  cent,  alcohol  and  the  phytosterol  crystallized  out.  The 
phytosterol  crystallized  in  well-marked  needle-shaped  crystals, 
occurring  in  tufts. 

RESULTS  OBTAINED. 

Wt.  oil.         Wt.  ether  residue.  Unsap.  matter. 
Grams.  Gram.  Per  cent. 

Phoenix  paint  oil 55-3945  0.7691  1.39 

Glucose  sugar  oil 49.1123  0.7036  1.43 

Average 1.41 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Unsap.  matter. 

Per  cent.  Observer.  Reference. 

1.35  Spiiller  Dingl.,  264, 626. 

1.55  Hart9  Chem.  Ztg.,  17,  1522. 

2.86  Hopkins  J.  Am.  Chem.  Soc.,  Dec.,  1898. 

1  Possible  traces  of  hydrocarbon  oils  neglected  by  this  method. 

2  Dark  brown  oil. 


24 
COLOR  REACTIONS  WITH  SULPHURIC  ACID. 

/.  Heydenreich"  s   Test. 

Process. — 20  drops  of  oil  were  placed  on  a  watch-glass  and  two 
drops  of  HSSO4,  sp.  gr.  1.84,  allowed  to  fall  into  center  of  oil. 
The  oil  and  acid  were  then  stirred  together  with  a  glass  rod. 

Results  Obtained. 

A.  Phoenix  Paint  Oil — Glucose  Sugar  Oil. — Before  stirring, 
rayed   ring   of    mahogany  red  on  golden-brown  baskground  ; 
after  stirring,  dark  red-brown  with  honey-like  consistency. 

B.  Distillery  Oil. — Before  stirring,  similar  to  result  with  the 
other  samples ;  after  stirring,  dull  claret  with  honey-like  con- 
sistency. 

II.   Carbon  Disulphide  Test. 

Process. — One  drop  concentrated  HaSO4  was  added  to  solu- 
tion of  a  few  drops  oil  in  CS8 ;  the  mixture  was  then  well  shaken 
and  allowed  to  stand  for  24  hours. 

Results  Obtained. 

A.  Phoenix  Paint   Oil — Glucose  Sugar   OH.  —  Golden-brown 
color  by  transmitted  light ;    mahogany-red  by  reflected  light. 
After  24  hours,  fine  violet. 

B.  Distillery  Oil. — Deep  claret  color ;    after   24   hours,  fine 
violet. 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

HNOj.  H,SO4.  Observer.  Reference. 

Yellow-orange         Duliere  J.  Pharm.  ( 1897),  217. 

Dark  red  Hart1  Chem.  Ztg. ,  17,  1522. 

Reddish  (Massie)  Black-brown  Shuttleworth  Pharm.  J.,  16,  1095. 

Reddish-yellow      Green  Brannt  An.  and  Veg.  Fats  and  Oils. 

COLOR  REACTIONS  WITH  NITRIC  ACID. 

/.  Hauchecorne'  s  Test. 

Process. — 3-5  parts  of  oil  by  volume  were  shaken  with  one 
part  HNO,,  of  sp.  gr  1.32.  Mixture  was  then  heated  on  water- 
bath  for  five  minutes  and  allowed  to  stand. 

Results  Obtained. 

A.  Phoenix  Paint  Co.  Oil — Glucose  Sugar  Oil. — Oily  layer 
orange  yellow  and  of  consistency  of  thick  honey. 

1  Dark  brown  oil. 


25 

B.  Distillery  Oil. — Oily  layer  mahogany  red  and  of  much  less 
viscosity. 

II.  Massifs  Test. 

Process. — 3  parts  oil  by  volume  were  shaken  with  one  part 
HNO3,  of  sp.  gr.  1.42,  for  two  minutes  and  allowed  to  stand. 

Results  Obtained. 

A.  Phoenix  Paint  Oil — Glucose  Sugar  Oil. — Oily  layer  bright 
mahogany  red,  solidifying  after  some  days. 

B.  Distillery  Oil. — Oily  layer  very  dark  reddish-brown  and  of 
consistency  of  strained  honey. 

///.   Glassner's  Test. 

Process. — Oil  was  cautiously  poured  into  equal  volume  of 
fuming  HNO3,  using  very  small  quantities. 

Results  Obtained. 

A.  Phoenix  Paint  Oil — Glucose  Sugar  Oil. — After  much  effer- 
vescence, oil  was  changed  to  pale  yellow  solid  with  rancid  odor. 

B.  Distillery  Oil. — After  much  effervescence,  oil  became  of  a 
brilliant  orange-yellow  and  of  the  consistency  of  thick  honey. 

SILVER  NITRATE  REDUCTION  TESTS. 
7.  Becchi's  Test. 

Process  of  Pearmain  and  Moor. — 10  cc.  oil  were  shaken  with  2 
cc.  of  a  reagent  prepared  by  dissolving  i  gram  of  AgNO3  in  100 
cc.  of  95  per  cent,  alcohol,  adding  20  cc.  ether  and  one  drop  of 
nitric  acid.  The  mixture  was  then  placed  in  boiling  water  for 
ten  minutes. 

Results  Obtained. 

Phoenix  Paint  Oil — Glucose  Sugar  Oil. — Dark  brown  coloration. 
Viscosity  increased. 

Distillery  Oil. — Dark  brown  coloration.  Viscosity  much  in- 
creased. 

II.  Brull^s  Test. 

Process. — 12  cc.  oil  were  shaken  with  5  cc.  of  solution  of  2.5 
grams  AgNO,  in  100  cc.  of  95  per  cent,  alcohol.  The  mixture 
was  then  heated  in  boiling  water  20  minutes. 


26 

Results  Obtained. 
All  three  oils  colored  intensely  black. 

MISCELLANEOUS  COLOR  REACTIONS. 

/.    Well-man's  Test. 

Process. — 2  cc.  of  freshly  made  phosphomolybdic  acid  were 
shaken  with  solution  of  25  drops  oil  in  5  cc.  chloroform.  A  few 
drops  of  NH4OH  were  then  added,  the  mixture  again  shaken 
and  allowed  to  separate. 

Results  Obtained. 

A.  Phoenix  Paint  Oil — Glucose  Sugar  Oil. — Very  dark  green 
upper  layer,  becoming  bright  blue  on  addition  of  NH4OH. 

B.  Distillery  OH. — Coloring  much  lighter  than  in  case  of  the 
other  two  oils. 

II.  Renard's  Test 

Process. — 10  cc.  of  reagent,  composed  of  equal  parts  SnBr4  and 
CS2,  were  shaken  with  5  cc.  oil. 

Results  Obtained. — Brown- violet  coloration,  with  slight  evolu- 
tion of  gas,  for  all  three  oils. 

///.  Hirschsohri's  Test. 

Process. — 6  drops  of  reagent,  made  by  dissolving  one  gram 
AuCl,  in  200  cc.  chloroform,  were  added  to  5  cc.  oil  and  well 
shaken. 

Results  Obtained. 

A.  Phoenix  Paint  Oil — Glucose  Sugar  Oil. — Pale-green  colora- 
tion. 

B.  Distillery  Oil. — Yellowish-brown  coloration. 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Becchi.  Bnille.         Wellman.  Observer.  Reference. 

Slightly  dark'd Green  ;  blue  NH3  Hart1          Chem.  Ztg.,  17,  1522. 

Faint  brown       Black De  Negri8  Chem.  Ztg.,  22, 961-976. 

ELAIDIN  REACTION. 

Pouters  Method. 
i  cc.  mercury  was  dissolved  in  12  cc.  cold  HNO,  of  1.42  sp.  gr. 

i  Dark  brown  oil.  2  Petroleum  ether  extract. 


27 

2  cc.  of  the  freshly  prepared  green  solution  were  added  to 
50  cc.  oil  contained  in  a  wide- mouthed,  stoppered  bottle,  the 
contents  of  the  bottle  violently  shaken  and  the  agitation  repeated 
every  ten  minutes  for  two  hours.  The  temperature  during  this 
operation  ranged  from  20°  C.  to  22°  C.  The  oil  was  then 
allowed  to  stand  undisturbed  in  a  warm  room. 

Results  Obtained. 

A.  Phoenix  Paint  Co.    Oil. — 2   hrs. — Orange-yellow  deposit, 
pastry  in  consistency  and  small  in  amount.     Orange-red,  honey- 
like  liquid  above. 

24  hrs. — Deposit  unchanged,  supernatant  liquid  of  less  vis- 
cosity and  darker  color. 

2  wks. — Little  change  except  in  gradual  darkening  of  liquid 
to  reddish-brown. 

B.  Chicago  Glucose  Sugar  Refining  Co.  Oil. — Reaction  similar 
to  that  with  Phoenix  Paint  Oil. 

C.  Distillery  Oil. — Reaction  similar  to  that  with  the  Phoenix 
Paint  Oil,  except  that  the  viscosity  of  the  supernatant  liquid 
was  less  and  its  color  darker.     After  two  weeks  no  difference 
could  be  detected  in  the  results  of  the  tests  on  the  oils. 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Result  of  test.  Observer.  Reference. 

Pasty  or  buttery  mass  Smith  J.  Soc.  Chem.  Ind.,  n,  504. 

Yellow-orange  color ;  partial 

solidification.  Shuttleworth  Pharm.  J.,  16,  1095. 

Yellow-orange ;  no  solidifica- 
tion. Duliere  J.  Pharm.  (1897),  217. 

Much  olein ;  bet.  olive  and 

cotton-seed  oils.  Lloyd  Chem.  Centrbl.,  59,  1193. 

DETERMINATION  OF  RISE  IN  TEMPERATURE  WITH  H,SO4. 

Maument  Test,  Archbutfs  Method. 

50  grams  oil  were  weighed  into  a  beaker  and  brought  to 
exactly  the  same  temperature  as  the  H,SO4  to  be  used  for  the 
test.  This  temperature  should  not  be  far  from  20°  C.  but  the 
exact  point  is  immaterial,  provided  it  is  uniform  for  both  oil  and 
acid.  The  beaker  of  oil  was  then  placed  in  an  asbestos  nest  and 
10  cc.  H,SO4,  of  1.842  sp.  gr,  by  Westphal  balance,  rapidly 
delivered  into  oil  from  a  pipette.  During  the  delivery  of  the 


28 

acid  and  thereafter,  the  mixture  of  oil  and  acid  was  vigorously 
stirred  with  a  thermometer  until  the  temperature  began  to  fall. 
A  record  was  taken  of  the  highest  temperature  shown  by  the 
thermometer.  The  rise  in  temperature  for  50  grams  distilled 
water,  under  exactly  the  same  conditions,  was  also  noted. 
Care  was  observed  that  the  examination  of  all  the  specimens  of 
oil  should  be  conducted  with  a  uniform  initial  temperature. 

Specific  Temperature. 

Rise  in  temperature  of  oil  as  compared  with  that  of  water, 
reckoned  as  100. 

RESULTS  OBTAINED. 

Initial  temp.  Av.  rise  in  temp.  Specific  temp. 

Distilled  water 23°  C.  42°  C.  100 

Phoenix  paint  oil 23°  C.  75°  C.  178.6 

Glucose  sugar  oil 23°  C.  74°  C.  176.2 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Maumen£  figure.  Observer.  Reference. 

56°  C.  Spiiller  Dingl.,  264,  626. 

60.5°  C.  Hart  Chem.  Ztg.,  17,  1522. 

79°  C.  Jean1  J.  Soc.  Chem.  Ind.,  n,  504. 

84°C.-89°C.  De  Negri  and  Fabris1  Ztschr.  anal.  Chem.,  33,  547-72. 

89°  C.  Mills2  J.  Soc.  Chem.  Ind.,  xx,  504-5. 

DETERMINATION  OF  HEAT  OF  BROMINATION. 

Process  of  Hehner  and  Mitchell. 

One  gram  of  oil  was  carefully  weighed  into  short  test-tube 
having  one-inch  bore.  This  tube  was  then  suspended  in  a 
beaker  by  means  of  a  large  cork  and  the  beaker  placed  in  an 
asbestos  case.  A  double  protection  was  thus  afforded  against 
the  radiation  of  heat. 

10  cc.  of  chloroform  were  next  added  to  the  oil  and  a  delicate 
thermometer  introduced  into  the  solution,  in  such  a  manner  that 
its  bulb  rested  at  about  the  center  of  the  liquid.  One  cc.  of 
bromine  was  then  added  to  the  dissolved  oil  and  the  rise  in  tem- 
perature noted.  Great  care  was  taken  that  the  oil,  chloroform 
and  bromine  should  all  be  of  the  same  temperature  before  begin- 
ning the  operation. 

i  Obtained  by  use  of  Jean's  Thermelaeometer. 
*  15  grams  oil  +  5  cc.  H,SO4. 


29 

Six  readings  were  taken  for  each  sample.     Glacial  acetic  acid 
was  used  as  the  diluent,  instead  of  chloroform,  in  the  case  of  the 
mixed  insoluble  fatty  acids.     The  calculated  iodine  value  was 
found  by  multiplying  the  bromine  thermal  value  by  5.5. 
RESULTS  OBTAINED. 

Br.  Thertn.  Val.  Hubl  No.  Calc.  I.  No. 

Phoenix  oil 21.9°  C.  1 19.74  120.45 

Glucose  sugar  oil 21.8°  C.  118.62  119.90 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Br.  Therm.  Val.    Calc.  I.  No.          Observer.  Reference. 

21.5  118.25  Hehner  J.  Soc.  Chem.  Ind.,  16,  87. 

DETERMINATION  OF  SOLUBILITY  IN  GLACIAL  ACETIC  ACID. 
Valenta1  s  Process. 

Three  cc.  glacial  acetic  acid  were  added  to  3  cc.  oil  in  a  wide- 
mouthed  test-tube.  The  mixture  was  then  gently  warmed  until 
the  oil  was  completely  dissolved,  a  thermometer  inserted  and  the 
oil  allowed  to  gradually  cool,  with  continual  stirring.  The  tem- 
perature at  which  permanent  turbidity  first  appeared  was  re- 
corded. 

Results  Obtained. 

A.  Phoenix  Paint  Co.  Oil. — 74°  C.,  average  of  six  tests. 

B.  Chicago  Glucose  Sugar  Refining  Co.   Oil. — 80°  C.,  average 
of  five  tests. 

C.  Distillery  Oil. — 44°  C.,  average  of  five  tests. 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 

Turbidity  temp.        '  Observer.  Reference. 

65°  C.  De  Negri1  Chem.  Ztg.,  22,  961-976. 

DETERMINATION  OF  OXYGEN-ABSORPTION. 
Livache's  Test. 

Finely  divided  lead  powder  was  obtained  by  precipitating 
metallic  lead  from  (CH3COO).,Pb  by  means  of  zinc,  washing  the 
precipitate  rapidly  with  water,  alcohol,  and  ether,  in  the  order 
named,  and  drying  it  in  a  desiccator. 

Approximately  one  gram  of  lead  powder,  prepared  as  above, 
was  spread  in  a  thin  layer  on  a  large  watch-glass  and  a  few 

1  Petroleum  ether  extract. 


30 

drops  of  oil  added  by  means  of  a  pipette,  care  being  taken  to 
keep  the  drops  of  oil  separate.  The  amount  of  oil  taken  was 
accurately  determined  and  was  not  allowed  to  exceed  0.6  gram. 
The  watch-glass  was  then  exposed  to  light  but  protected  from 
dust,  and  allowed  to  remain,  at  the  ordinary  temperature,  until 
it  ceased  to  gain  in  weight. 

The  total  gain  in  weight  and  the  time  required  for  this  gain, 
were  both  taken  into  account.  All  samples  tested  were  exam- 
ined at  same  time  and  under  identical  conditions. 

RESULTS  OBTAINED. 
A.  PHOENIX  PAINT  Co.  Oil,. 

Wt.  oil.  Total  gain.        Time  required.  Gain. 

Gram.  Gram.  Days.  Per  cent. 

0.5193  0.0310  7  5.97 

B.  CHICAGO  GLUCOSE  SUGAR  REFINING  Co.  Oil,. 
0.3313  0.0172  10  5.19 

PREPARATION  OF  INSOLUBLE  PATTY  ACIDS. 

The  mixed  insoluble  fatty  acids  were  prepared,  in  considera- 
ble bulk,  for  analysis,  by  a  process  analogous  to  that  used  in 
determining  the  Reichert  value,  except  that  no  attempt  was 
made  to  have  the  work  quantitative.  The  oil  was  saponified  by 
aqueous  KOH  in  considerable  excess,  the  soap  decomposed  by 
dilute  H2SO4  and  the  resultant  liquid  heated  until  the  oily  layer 
of  liberated  fatty  acids  became  clear  and  transparent.  The  whole 
mass  was  then  transferred  to  a  separating  funnel,  the  aqueous 
layer  drawn  off  and  the  fatty  acids  washed  with  boiling  water 
until  the  wash-water  was  neutral  to  litmus. 

The  insoluble  acids  were  then  subjected  to  a  steam  distillation 
at  the  ordinary  pressure  and  the  residue  washed  with  boiling 
water,  filtered  through  a  dry  filter  and  dried  at  100°  C.  Consid- 
erable difficulty  was  found  in  obtaining  uniform  samples  for 
analysis,  owing  to  the  sharp  separation  of  the  acids  into  a  solid 
and  a  liquid  portion. 

DETERMINATION  OF  MELTING-POINT. 

Method  of  La  Sueur  and  Crossley.1 
A  small  amount  of  the  mixed  insoluble  fatty  acids  was  intro- 

1  J.  Soc.  Chem.  Ind.,  Nov.  30,  1898. 


duced  into  a  thin-walled  test-tube  of  small  bore  and  the  test-tube 
attached  to  a  delicate  thermometer  by  means  of  rubber  bands. 
A  capillary  tube,  open  at  both  ends  and  having  an  internal 
diameter  of  not  more  than  three-fourths  of  a  millimeter,  was 
then  introduced  into  the  test-tube,  in  such  a  manner  that  one 
end  of  the  capillary  dipped  below  the  surface  of  the  solidified 
fat.  The  whole  apparatus  was  then  introduced  into  a  beaker 
filled  with  cold  water  and  the  temperature  of  the  water  very 
gradually  raised. 

Melting-point. 
Temperature  at  which  liquid  rises  in  the  capillary  tube. 

DETERMINATION  OF  SAPONIFICATION  VALUE. 

A.  Method  by  Titration. 

5-10  grams  of  mixed  insoluble  fatty  acids  were  weighed  into 
a  small  flask,  dissolved  in  carefully  neutralized  alcohol  by  heat- 
ing on  the  water-bath  and  titrated,  while  still  warm,  with 
n/KOH. 

B.  Koettstorfer  Method. 

As  a  confirmatory  test,  the  saponification  value  was  also  found 
by  the  ordinary  Koettstorfer  method  used  in  the  case  of  the 
original  oil. 

Mean  Molecular  Weight  of  Fatty  Acids. 

This  value,  also  known  as  the  "Mean  Combining  Weight," 
is  equal  to  the  number  of  milligrams  of  fatty  acids  neutralized  by 
i  cc.  of  rc/KOH. 

The  ' '  Saponification  Equivalent ' '  of  fatty  acids  is  identical 
with  their  mean  molecular  weight.  This  is  not  true  in  the  case 
of  neutral  oils. 

Determination  of  Constants? 
A.  SPECIFIC  GRAVITY. 

Wt  acids  at  100°  C.       Wt.  water  at  15.5*  C.  Sp.  gr.  acids 

Gram.  Gram.  at  100°. 

1 0.3250  0.3811  0.8528 

II 0.6780  0.7947  0.8530 

Average 0.8529 

1  The  fatty  acids  examined  were  prepared  from  the  Glucose  Sugar  Refining  Com- 
pany's oil. 


32 
B.    MEI/TING-POINT. 


C.  IODINE  ABSORPTION. 

A^UA     LC3LO. 

Wt.  mixed  acids.      Vol.  hypo.l            Wt.  iodine. 

Iodine  abs. 

Gram.                      cc.                        Gram. 

Per  cent. 

I 

__    .                      _/r    .                      „  iiroft 

JI  

'    O'^/y^-                     ^0.4                     o.  3oD-^ 
O  2  S  2  ^                     244                     O  ^0088 

122  8 

HI  

O  I7S2                     l6  7                     O  2I2OQ 

IV 

•    0.3156                      29.8                      0.37846 

II9.9 

Average 

TTiiHI  ficnirp 

Q 

» 

D.  HEAT  OF  BROMINATION. 

Br.  Therm.  Val.                    Hiibl  No. 

Calc.  I.  No. 

Fatty  acids  •  •  • 

•  •  •  •  •   21  6°  C                          1  20  08 

118.80 

E.  SAPONIFICATION  VALUE. 

Wt.  acids.    Vol.  n/KOHbyUtr.    Saponifi- 

Mean 

Grams.                    cc.                  cation  val. 

combin.  wt. 

I 

•    7-0294                   25.0                   199.52 

281.17 

II    

c  6080                       IQ  7                       IQ7  06 

0   .      ~ 

By  Koett. 

^04.70 

Ill 

.    1.8415                     6.5                   198.02 

283.30 

IV 

1.4302                        5.15                   202.01 

277.71 

Average 

-78T    TJ 

COMPARISON  WITH  RESULTS  OF  OTHER  OBSERVERS. 
B.    MELTING-POINT. 

Melting-point  acids.  Observer.  Reference. 

10.5°  C.-I2.20  C.  Hoppe-Seyler2          Bull.  Soc.  Chim.  (1866),  [2]  6,  342. 

i6°C.-i8°C.  Duliere  J.  Pharm.  (1897),  217. 

18°  C.-200  C.  DeNegriandFabris  Ztschr.  anal.  Chem.,  33,  547. 

20°  C.  Jean  J.  Chem.  Soc.  Ind.,  u,  504. 

39-5°  C.  De  Negri3  Chem.  Ztg.,  22,  961-976. 

C.  IODINE  ABSORPTION. 

Hiibl  No.  acids.  Observer.  Reference. 

ii3-"5  DeNegriandFabris  Ztschr.  anal.  Chem.  33,  547. 

123.27  De  Negri3  Chem.  Ztg.,  22,  961. 

125  Spiiller2  Dingl.,  264, 626. 

I26-4  Hopkins  J.  Am.  Chem.  Soc.,  Dec.,  1898. 

E.  SAPONIFICATION  VALUE. 


Sapon.  value.  Mean  mol.  ' 

198.4  282.76 

1  24.8  grams  per  liter. 


Observer.  Reference. 

Hart  Chem.  Ztg.,  6,  1522. 

2  Ether  extract. 


8  Petroleum  ether  extract. 


33 

A  METHOD   FOR  THE   IMPROVEMENT   OF  MAIZE   OIL  BY  THE  USE 
OF  STEAM. 

Introductory  Statement. — As  developed  in  the  course  of  the 
preceding  analysis,  the  oil  of  maize  has  several  objectionable 
properties,  which  tend  to  injure  it  commercially  for  uses  for 
which  it  would  be  otherwise  well-fitted.  Among  the  most 
important  of  these  properties  are  the  following : 

1.  The  pronounced  grain-like  odor  and  the  acrid  after-taste  of 
the  oil.     These  qualities  unfit  it  for  use  as  a  salad  oil. 

2.  The  rather  high  percentage  of  free  acid  and  the  marked 
action  which  the  oil  has  on  metal.     These  qualities  lessen  its 
value  as  a  lubricating  oil. 

3.  The  slowness  with  which  the  oil  absorbs  oxygen,   even 
under  the  influence  of  dryers.     This  militates  against  its  use  as 
a  paint  oil  or,  at  best,  permits  it  to  be  used  only  in  a  cheap 
grade  of  paint. 

It  was  with  the  idea  of  improving  maize  oil  in  one  or  more  of 
these  directions  that  it  was  subjected  to  a  prolonged  treatment 
with  steam.  A  somewhat  extended  study  of  the  work  of  other 
observers  on  this  oil,  fails  to  reveal  any  attempt  to  modify  the  oil 
in  this  way.  It  therefore  seems  a  fair  conclusion,  to  claim  that 
the  application  of  steam  distillation  to  maize  oil,  for  the  purpose 
of  improving  it  commercially,  is  a  new  method. 

Description  of  Process. — A  fresh  sample  of  the  oil,  as  expressed 
from  the  germ  by  hydraulic  pressure,1  was  subjected  to  a  brisk 
steam  distillation  for  about  eight  hours.  Just  enough  heat  was 
used  under  the  oil  to  prevent  condensation  and  the  steam  was 
used  at  the  ordinary  pressure. 

The  odor  of  the  volatile  oil  was  very  marked,  particularly  at 
the  begining  of  the  operation,  and  a  portion  of  this  oil  was  after- 
ward recovered  from  the  distillate. 

Considerable  dissociation  of  the  lower  esters  took  place  and 
large  quantities  of  a  solid  fatty  acid,  volatile  to  some  extent  in 
steam  but  insoluble  in  water,  collected  in  both  the  retort  and  the 
receiver. 

At  the  close  of  the  operation,  the  liquid  in  the  distilling  flask 
was  transferred  to  a  separating  funnel,  the  aqueous  layer  drawn 
6ff  and  the  oil  washed  repeatedly  with  boiling  water.  The  oil 

1  From  the  Chicago  Glucose  Sugar  Refining  Co. 


34 

was  then  allowed  to  stand  for  sometime  in  the  separating  funnel 
in  order  that  the  water  might  drain  out.  After  as  complete 
separation  as  could  be  effected  in  this  way,  CaCL,  was  added  to 
the  oil  and  the  drying  completed.  The  oil  was  then  filtered 
through  a  dry  filter  until  bright  and  clear  and  the  constants 
determined  in  the  usual  manner. 

Determination  of  Constants. 
A.  SPECIFIC  GRAVITY. 


I  

Wt.  water                 Wt.  oil                   Wt.  oil 
15.5°  C.                    15.5°  C.                     100°  C.                    Sp.  gr. 
Grains.                   Grains.                  Grams.                   15.5°  C. 

Sp.  gr. 
too"  C. 

0.8729 
0-8733 
0.8731 

Degrees 
acidity. 

3-05 
3.01 

3-°3 

Ether 
value. 
186.51 
189.14 
187.83 

Iodine  abs. 
Per  cent. 

112.93 
US-OS 
II3-03 
112.03 
.    112.76 

Acetyl 
figure. 
12.3 
12.  0 
12.15 

mp. 

II 

I 

1^152                        4                   .                       0.9  3 

B.  FREE  ACID. 

Wt.oil.   Vol.  «/10KOH.      Acid          Free  acid. 
Grams.               cc.              value.          Per  cent. 

II 

I 

C.  SAPONIFICATION  VALUE. 

Wt.  oil.             Vol.  «/HCl.        Koettstorfer              Sapon. 
Grams.                      cc.                         fig.                        equiv. 

II  

I. 

D.  IODINE  ABSORPTION. 

Wt.  oil.           Vol.  hypo.               Wt.  iodine. 
Gram.                     cc.                        Gram. 

II.  . 

III. 

5                    22.9               0.2  5124 

IV. 
I 

E.  ACETYI.  VALUE. 

Wt.oil.            Vol.n/HCl.        Koettstorfer  Vol.  n/10KOH. 
Grams.                    cc.                        fig.                         cc. 

II 

F.  MAUMENE  FIGURE. 

Initial  temp.                      Av.  rise  in  temp.                     Specific  te: 

23°  C.                             77°  C.                             183.3 

35 
G.  BROMINE  THERMAL  VALUE. 

Br.  thermal  val.  Hiibl  No.  Calc.  iodine  No. 

20.4°  C.  112.76  112. 2O 

H.  VISCOSITY. 

Tempera-       Av.  time  of  flow.         Viscosity.  Viscosity, 

ture.  Seconds.  Water.  Rape  oil. 

20°  C.  310.2  10.70  76.50 

K.  INDEX  OF  REFRACTION. 

Temperature.  A.  T. 

1 15°  C.  1.4765  35-7 

II 15°  C.  1.4766  35-8 

III 15°  C.  1.4766  35.8 

Average  for  15°  C 1.4766  35.8 

L.  SOLUBILITY  IN  GLACIAL  ACETIC  ACID. 

Valenta  value  =  60°  C Average  of  four  tests. 

M.  SILVER  NITRATE  REDUCTION  TESTS. 

Becchi's  test Dark  brown  coloration. 

Brulte's  test Black  coloration. 

N.  OXYGEN  ABSORPTION  BY  LIVACHE  TEST. 

Wt.  oil.  Total  gain.       Time  required.  Gain. 

Gram.  Gram.  Days.  Per  cent. 

0.3005  0.0105  4  3-50 

Effect  of  Treatment  as  Shown  by  Comparison. — In  instituting 
this  comparison,  reference  is  made  only  to  the  sample  from  the 
Glucose  Sugar  Refining  Co.,  since  it  was  this  oil  which  was 
chosen  as  the  subject  for  experiment. 

A  tabulation  of  the  constants  of  the  steamed  oil,  together  with 
those  of  all  other  samples  examined,  will  be  given  in  the  sum- 
mary of  this  dissertation,  but  the  main  points  of  difference 
between  the  treated  and  untreated  oils  will  be  noted  here. 

1.  The  steamed  oil  is  notably  lighter  in  color  than  that  not  so 
treated. 

2.  The  odor  and  taste  of  the  volatile  oil  are  entirely  lacking 
in  the  modified  oil,  which  is  absolutely  neutral  in  these  respects. 

3.  The    specific    gravity    and    acetyl  value    are    somewhat 
increased,    but   not  to   the   extent  which   might   naturally  be 
expected. 

4.  The  percentage  of  free  acid  is  notably  decreased,  this  con- 
stituting a  marked  improvement  in  the  oil. 


36 

5.  The  solubility  of  the  oil  in  alcohol  and  in  acetic  acid  is 
noticeably  increased. 

6.  The  iodine  absorption,  bromine  thermal  value  and  absolute 
amount  of  oxygen  absorption  are  all  decreased,   but  the  total 
time  required  for  drying  is  much  lessened.      The  drying  quali- 
ties of  the  oil  are,  therefore,   on  the  whole,  considerably  im- 
proved. 

Further  investigation  is  needed  as  to  length  of  treatment, 
effect  of  age  on  the  modified  oil  and  several  other  points,  but 
enough  work  has  been  done  to  show  that,  by  the  process  in 
question,  maize  oil  is  much  improved  for  use  as  a  salad  oil,  a 
lubricant,  or  even  as  a  paint-oil. 


PART  III— SUMMARY. 

DESCRIPTION  OP  SAMPLES. 
/.   Chicago  Glucose  Sugar  Refining  Co.  Oil. 

This  oil  is  a  freshly  made,  pale  yellow  sample  of  maize  oil,  as 
expressed  from  the  germ  by  hydraulic  pressure,  and  illustrates 
the  ordinary  commercial  product. 

//.  Phoenix  Paint  Co.  Oil. 

This  specimen  is  a  ten-year-old  sample  of  maize  oil,  which 
was  also  obtained  by  expression  from  the  germ,  and  which  has 
been  preserved  from  the  action  of  light  and  air.  It  serves  to 
illustrate  the  changes  in  the  oil  which  are  due  to  age. 

///.  Distillery  Oil. 

This  oil  is  a  golden-brown  sample  of  maize  oil  from  the  mash 
of  a  distillery  and  is  approximately  fifteen  years  old.  As  will 
be  seen  from  an  examination  of  its  constants,  it  is  practically  a 
distinct  oil  from  that  prepared  by  hydraulic  pressure.  For  this 
reason,  its  examination  was  abandoned  after  the  determination 
of  its  more  important  constants. 

IV.  Insoluble  Fatty  Acids. 

This  sample  was  prepared  from  the  Glucose  Sugar  Co.  oil  by 
a  method  given  in  detail  on  page  30  of  this  dissertation. 

V.  Steamed  Maize  Oil. 

A  full  description  of  this  modification  of  maize  oil,  together 
with  its  mode  of  preparation,  will  be  found  on  pages  33-36. 


453070 


o  ^  _     ^ 

l?1?t? 


«   .  O*  .   .   .   .  <-» 

£ :  1?  i  ;  ;  ;\ 

7i  '  d  S 


sod 


000000 


>   ,SH  H- 

.ti  .t!  o  o  w> 
«  «  M  u  o 

JiJli 

>  >  5  a  I 


39 


fog* 

£   o    to  M 


•H       M       O       M 


40 


3 

a 

0) 

•s 

'  J  "o 

.  CJ  to05  0 

"5- 

i 

3 

Q 

•  °^  <x  "^  °o 
fe«   o- 

a 
1 

i 

0 

*l 

M        * 

13 

cr 

O1 

u 

v 

,13 

a 

:EI<I<ANEOUS. 

Distillery  oil. 

Mahog.  to  claret 

Tf 

a 

tJ 
ID 
> 

« 

Mahogany 

a 
=: 
o 

u. 

X! 

1 
^ 

rt 

Q 

li 

-Is 

H5 

2  Q 
O 

;jht  green  and  bl 

Brown-violet 

a 
•f 

0 

| 
1 

13     '.      ',     '.   o 

if  '  '  '  ^ 
1 

(LI 

be 

i 

ft 

^S 
r; 

'3 

*\ 

0 

*2 

« 

. 

£ 

a 

2 

a 

5 

rti 

% 

3 

.a 

9- 

5 

Jf 

ed 

8 

'S 
g 

1 

S 

H3 

_bf 

^%S-^% 

a 

| 

^ 

rt 

° 

E 

s  1 

_o 

"S 

a 

'« 

£ 

^ 

"o 

^ 

a1 

o   °  ^ 

1 

.2 

^ 

a 

u> 

w 

S 

> 

u 

& 

^  2  - 

a 

& 

tx 

m 

a 

S 

1 

S 

>-, 

a 
?, 

a 

1 

a 

1 

^  p 
ft 

reen  cha 

'<? 
o 

« 

£ 

lo^fco" 

O 

a 

« 

a 

6< 

a 

4> 

fcjO 

«  ***    s 

J-! 

C 

'C 

^ 

a 

M 

* 

0 

1 

O 

^ 

a 

O 

-n 

A  & 

c6 

M* 

rt 

g§  = 

Heydenreich—  H2SO 

Carbon  disulphide  — 

Hauchecorne—  HNO 

0 

i 
I 

Glassner—  HNO3 
Becchi—  AgNOj 
Brull6—  AgNOs 

Wellman—  Phos.  mo 

Renard  —  SnBr4 

Hirschsohn  —  AuCls 

El  aid  in  test 
Maumene"  —  Rise  in  t 
Maumene"  —  Specific 
Bromine  thermal  va 
Valenta's  test 

Livache  test  —  Per  cei 

MATHEMATICAL  CALCULATIONS. 

By  means  of  the  following  calculations,  an  attempt  has  been 
made  to  show  that  the  results  of  the  preceding  analysis  are 
consistent  and  that,  at  most,  the  difference  between  the  observed 
and  the  calculated  amounts  is  well  within  the  bounds  of  experi- 
mental error. 

The  mean  molecular  weight  of  each  class  of  fatty  acids  and 
their  relative  amounts,  are  also  here  derived.  In  this  way  an 
idea  is  gained  as  to  the  constitution  of  the  oil,  which  may  serve 
as  the  basis  of  further  investigation. 

/.  Determination  of  Glycerine. 

Assume  R  =  radicle  of  fatty  acid  =  e.  g.  C18H36O  =  radicle  of 
C18H3602. 

.-.  C3H6O3.RS=  (ROH)3.C3H,  ^triglyceride. 
Assume  M  =  molecular  weight  of  ROH. 

. •.   3M  -f-  38  =  molecular  weight  of  triglyceride. 

Reaction  for  Saponijication. — 

C3H60S-R3  +  3KOH  =  3ROK  +  C3H6(OH)3. 
Assume  E  =  ether  value  of  glucose  oil. 

E  X  mol.  wt.  glycerine  X  100 

.'.  Per  cent,  glycerine  =  —  —  =  10.41. 

3  X  mol.  wt.  KOH  X  1000 

Per  cent,  glycerine  actually  recovered  =  10.35. 

//.  Determination  of  Total  Fatty  Acids . 

A  neutral  glyceride  may  be  considered  as  made  up  of  three 
molecules  of  a  fatty  acid  and  one  group  C3H2.  The  component 
parts  of  any  oil  are,  therefore, 

1 .  Total  fatty  acids. 

2.  f  |  of  total  amount  of  glycerine. 

3.  Unsaponifiable  matter. 

.*.  100  grams  maize  oil  =  F  grams  total  acid  -{- 

Calc.  glyc.  Unsap.  mat. 

ff  X  10.41  grams  +  1.43  grams. 
.'.  Per  cent,  total  fatty  acids  —  94.27. 


42 
///.   Determination  of  Volatile  Acids. 

Observed  Hehner  value  =  92.23 

.'.  Per  cent,  volatile  acids  =  94.27 — 92.23  =  2.04. 

IV.  Molecular  Weight  of  Total  Adds. 
Observed  saponification  equivalent  =  291 .22. 

.'.  Mol.  wt.  total  acids  — 291.22  X  0.9427  =  274.533. 

V.  Molecular  Weight  of  Volatile  Acids. 

Per  cent,  total  acid  Per  cent,  insol.  acid         , 


Mean  mol.  wt.  total  acid       Mean  mol.  wt.  insol.  acid 

Per  cent.  vol.  acid 


Mean  mol.  wt.  vol.  acid' 

.      94.27    _     92.23 2.04 

274.533         281.72        Mol.  wt.  vol.  acids' 
.'.  Mean  mol.  wt.  volatile  acids  =  127.5. 

VI.  Determination  of  Reichert  Figure. 
Reaction  between  KOH  and  fatty  acid  is  of  the  form 

ROH  +  KOH  =  ROK  +  H,O. 
.'.  Wt.  KOH  equivalent  to  volatile  acids  from  2.5  grams  oil  is 

5.61  X  0.0204  X  2.5 

I2y.5  =0.02244  gram. 

.'.  Calculated  Reichert  figure  =  4. 
Observed  Reichert  figure  =  4.2. 

Consistency  of  Observed  Constants. 

1.  Since  the  calculated  percentage  of  glycerine  is  dependent 
on  both  the  acid  value  and  the  Koettstorfer  figure,  the  consis- 
tency of  these  values  with  each  other  and  with  the  observed  gly- 
cerine content  may  be  considered  proved . 

2.  The  close  agreement  between  the  calculated  and  observed 
Reichert  figures   further  demonstrates  the   correctness  of  the 
Hehner  value,  the  Koettstorfer  value,  the  molecular  weight  of 
the  insoluble  acids  and  the  percentage  of  unsaponifiable  matter. 

3.  The  harmony  between  the  bromine  thermal  values  and  the 
Hiibl  figures  is  evidence  of  the  correctness  of  these  constants  as 


43 

observed.     The  consistency  of  the  following  observed  constants 
may  therefore  be  assumed  to  be  established. 

1.  The  acid  value. 

2.  The  Koettstorfer  figure. 

3.  The  percentage  of  glycerine. 

4.  The  Hehner  value. 

5.  The  Reichert  figure. 

6.  The  molecular  weight  of  the  insoluble  fatty  acids. 

7.  The  percentage  of  unsaponifiable  matter. 

8.  The  bromine  thermal  value. 

9.  The  Hiibl  figure. 

PERCENTAGE  COMPOSITION  OF  MAIZE  Oil,. 

Neutral  glycerides 97-4418 

Free  acid 1.1280 

Unsaponifiable  matter 1.4300 

99.9998 
CLASSIFICATION  OF  PATTY  ACIDS  OF  MAIZE  On,. 

Per  cent.  Mean  mol.  vrt. 

Total  acids 94-27  274.533 

Insoluble  acids 92.23  281.720 

Volatile  acids 2.04  127.500 


PART  IV.— BIBLIOGRAPHY. 

CHRONOLOGICAL  L,IST  OF  REFERENCES. 

1823. 

Title. 

Bizio :  Das  maiskorn. 
Original  Article. 

Chem.  und  Phys.  (Schweiger),  37,377. 

1832. 

Title. 

Brennol  aus  mais  [abs.]. 
Original  Article. 

Recueil  industrial,  Dec.,  1832. J 
Cross  Reference. 

Dingler's  Polytechnisches  Journal,  48,  (1833),  158. 

1866. 

Title. 

Hoppe-Seyler :  Composition  des  grains  de  mais. 
Original  Article. 

Bull.  Soc.  Chim.,  6,  [2],  342. 
Cross  References. 

Ztschr.  Chem.,  10,  (1867),  32. 

Jbs.  Fortschritte  der  Chem.,  20,  (1866),  698. 

71*. 

Allemann  :  Das  Fettig  Maisol. 
Original  Article. 

Wien.  Acad.  Ber.,  46,  [2],  185. J 
Cross  References. 

Jbs.  Fortschritte  der  Chem.,  21,  (1867),  765. 

Chem.  Ctrbl.,  12,  [2],  (1867),  1024. 

1880. 

Title. 

Schulz  :  Die  maisolgewinnung  aus  der  maismaische. 
Original  Article. 

Neues  Bren.  Fachbl.,  6,  No.  I.1 
Cross  Reference. 

Chem.  Ctrbl.,  12,  [2],  (1881),  48. 
1  Not  verified. 


45 

1881. 

Title. 

Leeuw  :  Method  of  Freezing  Maize  from  Fat. 
Original  Article. 

Bied.  Centr.,  1881,  702.'. 
Cross  Reference. 

J.  Chem.  Soc.  42,  A  (1882),  348. 

1885. 

Title. 

Maisch  :  Gleanings  in  Materia  Medica. 
Original  Article. 

Am.  J.  Pharm.,  57,  404. 

1886. 

Title. 

E.  B.  Shuttleworth  :  Notes  on  Maize  Oil. 
Original  Article. 

Canadian  Pharmaceutical  Journal,  June,  1886.' 
Cross  Reference. 

Pharm.  J.,  16,  (1886),  1095. 

Oil,  Paint  and  Drug  Reporter,  29,  (1886),  June  9,  41. 

Oil,  Paint  and  Drug  Reporter,  31,  (1887),  May  4,  37. 

1887. 

Title. 

Spiiller  :  Zur  Kenntniss  des  Sonnenblumen  und  Maisoles. 
Original  Article. 

Dingler's  Polytechnisches  Journal,  264,  626. 
Cross  References. 

Ztschr.  anal.  Chem.,  29,  (1890),  95. 

J.  Soc.  Chem.  Ind.,  13,  (1894),  257. 

Jsb.  Chem.,  41,  (1887),  2681. 

1888, 
Title. 

J.  U.  Uoyd :  Maize  Oil. 
Original  Article. 

Drug.  Circ.,  32,  209. 
Cross  References. 

Am.  J.  Pharm.,  60,  (1888),  325. 

Chem.  Ctrbl.,  59,  (1888),  1193. 

Pharm.  J.,  19,  [3],  (1888),  66-67. 

Jsb.  Chem.,  42,  (1888),  2846. 

Drug.  Circ.,  37.  (1893),  254. 

1888. 

Title. 

Hazura :  Zur  Kenntniss  der  nicht  trocknenden  Oele. 

1  Not  verified. 


46 

Original  Article. 

Ztschr.  angew.  Chem.,  (1888),  692. 
Cross  Reference. 

Jsb.  Chem.,  42,  (1888),  2382. 

1889. 

Title. 

Kennedy :  Use  of  Oil  of  Maize  in  Pharmacy. 
Original  Article. 

Pharm.  Record,  9,  284. 
Cross  References. 

Am.  J.  Pharm.,  61,  (1889),  442. 

J.  Pharm.,  21,  [5],  (1890),  564. 

Jsb.  Chem.  Tech.,  35,  (1889),  1185. 

1889. 

Title. 

Bowers  :  Oil  of  Maize. 
Original  Article. 

Pharm.  J.,  20,  Nov.  23,  1889. 
Cross  References. 

Am.  J.  Pharm.,  61,  (1889),  503. 

Oil,  Paint  and  Drug  Reporter,  36,  (1889),  Oct.  16,  57. 

1889. 

Heinitsh :  Maize  Oil. 
Original  Article. 

Pharm.  Record,  9,  (1889),  236. 
Cross  References. 

Am.  J.  Pharm.,  61,  (1889),  442. 

J.  Soc.  Chem.  Ind.,  12,  (1893),  607. 

Oil,  Paint  and  Drug  Reporter,  36,  (1889),  Aug.  10,  7. 

1891. 

Title. 

Advantages  Claimed  for  Corn  Oil. — [ED.] 
Original  Article. 

Oil,  Paint  and  Drug  Reporter,  40,  Oct.  12,  7. 

1892. 

Title. 

De  Negri  and  Fabris  :  Die  Oele. 
Original  Article. 

Rom.  Labor.  Chem.  Centrale  del  Gabelle,  1891-2,  222-225. 
Cross  References. 

Ztschr.  anal.  Chem.,  33,  (1894),  547-572. 

V.  Fort.  Chem.,  10,  (1895),  180. 

J.  Soc.  Chem.  Ind.,  12,  (1893),  607. 

Am.  Drug.,  23,  (1893),  221. 
i  Not  verified. 


47 

1892. 

Title. 

J.  Cruickshank  Smith  :  On  Maize  or  Corn  Oil. 
Original  Article. 

Oil,  Paint  and  Drug  Reporter,  42.  Aug.  i,  37. 
Cross  References. 

J.  Soc.  Chem.  Ind.,  n,  (1892),  504-505. 

Chem.  Ctrbl.,  63,  [2],  (1892),  317. 

Am.  J.  Pharm.,  64,  [2],  (1892),  433. 

1893. 
Title. 

Smetham :  Notes  on  Rice  Oil  and  Maize  Oil. 
Original  Article. 

Analyst,  18,  191-193. 
Cross  References. 

J.  Soc.  Chem.  Ind.,  12,  (1893),  848. 

Chem.  Ctrbl.,  64,  [2],  (1893),  599. 

Chem.  Ztg.,  17,  (1893),  1838. 

1893. 

Title. 

Patents  Controlling  Use  of  Corn  Oil  for  Paints.— [ ED.] 
Original  Article. 

Oil,  Paint  and  Drug  Reporter,  44,  Sept.  20,  5  and  18. 

1893. 

Title. 

Hart :  Baumwollstearin  und  maisol. 
Original  Article. 

Chem.  Ztg.,  17,  1522. 
Cross  References. 

J.  Soc.  Chem.  Ind.,  13,  (1894),  257. 

Anal.,  19,  (1894),  42. 

Chem.  Ctrbl.,  64,  (1893),  1093. 

1894. 

Title. 

Rokitianski :  Untersuchung  des  Fette  des  maismehles. 
Original  Article. 

Pharm.  Zeit.  fur  Russland,  33, 
Cross  References. 

V.  Fort.  Chem.,  10,  (1895),  22. 

Chem.  Ctrbl.,  66,  [2],  (1895),  22. 

J.  Chem.  Soc.,  68  A,  (1895),  501. 

Chem.  Ztg.,  18,  (1894),  804. 
1  Not  verified. 


48 

1895. 

Title. 

Concerning  Corn  Oil. — [Eo.] 
Original  Article. 

Oil,  Paint  and  Drug  Reporter,  68,  Dec.  2,  5. 

1897. 

Title. 

Duliere  :  I/huile  de  tnais. 
Original  Article. 

J.  Pharm.,  6,  [2],  217, 
Cross  Reference. 

V.  Fort.  Chem.,  12,  (1897),  194. 

1898. 

Title. 

De  Negri :  Der  Paradiesnussol,  der  Brasilienische  nussol,  dasmaisol. 
Original  Article. 

Chem.  Ztg.,  22,  961-976. 
Cross  Reference. 

Anal.,  24,  (1899),  274. 

1898. 

Title. 

C.  G.  Hopkins  :  The  Oil  of  Corn. 
Original  Article. 

J.  Am.  Chem.  Soc.,  Dec.,  1898. 


LIST  OF  PERIODICALS  AND  ABBREVIATIONS. 

I.  American  Druggist  and  Pharmaceutical  Record. 

1893-1897.  Am.  Drug. 

II.  Americal  Journal  of  Pharmacy. 

1824-1898.  Am.J.  Pharm. 

III.  Analyst. 

1877-1898.  Anal. 

IV.  Annalen  der  Chemie  und  Pharmacie. 

1832-1896.  Ann.  Chem. 

V.  Annales  de  chimie  et  de  physique. 

1789-1882.  Ann.  de  Chim. 

VI.  Bulletin  de  la  Socie"te"  chimique  de  Paris. 

1860-1898.  Bull.  chim. 

VII.  Chemisches  Centralblatt. 

1830-1898.  Chem.  Ctrbl. 

VIII.  Chemie  und  Physik  (Schweiger). 

1811-1830.  Chem.  und  Phys. 

IX.  Comptes  Rendus  hebdomadaires  des  Seances. 

1835-1897-  C.  R. 


49 

X.  Chemiker  Zeitung. 

1882-1898.  Chem.  Ztg. 

XI.  Druggist's  Circular  and  Chemical  Gazette. 

1874-1897.  Drug.  Circ. 

XII.  Dingler's  Poly technisches  Journal. 

1820-1898.  Dingl. 

XIII.  Journal  of  the  Chemical  Society  of  London. 

1848-1898.  /.  Chem.  Soc. 

XIV.  Journal  of  the  American  Chemical  Society. 

1878-1898.  /.  Am.  Chem.  Soc. 

XV.  Journal  de  pharmacie  et  de  chimie. 

1865-1898.  /.  Pharm. 

XVI.  Journal  of  the  Society  of  Chemical  Industry. 

1882-1898.  /.  Soc.  Chem.  Ind. 

XVII.  Jahresbericht  der  chemisches  Technologic. 

1855-1897.  Jsb.  chem.  Tech. 

XVIII.  Jahresbericht  iiber  die  Portschritte  der  Chemie. 
1847-1890.  Jsb.  Chem. 

XIX.  Oil,  Paint  and  Drug  Reporter. 

1881-1898.  Oil  Rep. 

XX.  Pharmaceutical  Record. 

1884-1892.  Pharm.  Rec. 

XXI.  Pharmaceutical  Journal. 

1841-1890.  Pharm.  J. 

XXII.  Vierteljahresschrift  iiber   die    Fortschritte  der  Chemie  der  Nah- 

rungs  und  Genussmittel. 
1886-1897.  V.  Fort.  Chem. 

XXIII.  Zeitschrift  fur  analytische  Chemie. 

1862-1898.  Ztschr.  anal.  Chem. 

XXIV.  Zeitschrift  fur  angewandte  Chemie. 

1888-1897.  Ztschr.  angew.  Chem. 

XXV.  Zeitschrift  fur  Chemie. 

1858-1871.  Ztschr.  Chem. 


BIOGRAPHICAL. 

Harriet  Winfield  attended  the  Jersey  City  High  School  for 
four  years  and  Wellesley  College  for  four  years.  At  Columbia 
University,  New  York,  she  studied  under  the  Faculty  of  Pure 
Science  during  the  years  1895-6,  '96-7,  '97-8,  and  '98-9. 

During  the  year  1896-97  she  held  the  Curtis  Graduate  Schol- 
arship from  Barnard  College. 

She  received  the  degree  of  Bachelor  of  Arts  from  Wellesley 
College  in  1887,  and  that  of  Master  of  Arts  from  Columbia 
University  in  1896. 


UNIVERSITY  OF  CALIFORNIA,  LOS  ANGELES 

THE  UNIVERSITY  LIBRARY 
This  book  is  DUE  on  the  last  date  stamped  below 


7  OPCALIFC 

LOS  ANGELES 
LIBRARY 


A    001  188442     6 


TP 

684 

C8W7 


